EP3464437A1 - Fibre reinforcement of reactive foams obtained by a moulding foam method - Google Patents

Fibre reinforcement of reactive foams obtained by a moulding foam method

Info

Publication number
EP3464437A1
EP3464437A1 EP17723145.3A EP17723145A EP3464437A1 EP 3464437 A1 EP3464437 A1 EP 3464437A1 EP 17723145 A EP17723145 A EP 17723145A EP 3464437 A1 EP3464437 A1 EP 3464437A1
Authority
EP
European Patent Office
Prior art keywords
fiber
reactive
foam
layer
reactive foam
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP17723145.3A
Other languages
German (de)
French (fr)
Other versions
EP3464437B1 (en
Inventor
Holger Ruckdaeschel
Alexandre Terrenoire
Rene ARBTER
Bangaru Dharmapuri Sriramulu Sampath
Peter Gutmann
Ragnar STOLL
Christophe HEBETTE
Robert Stein
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP3464437A1 publication Critical patent/EP3464437A1/en
Application granted granted Critical
Publication of EP3464437B1 publication Critical patent/EP3464437B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

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    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/36After-treatment
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04Polyurethanes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04Polyurethanes
    • C08J2375/08Polyurethanes from polyethers
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/70Wind energy
    • Y02E10/72Wind turbines with rotation axis in wind direction
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/70Wind energy
    • Y02E10/74Wind turbines with rotation axis perpendicular to the wind direction

Definitions

  • the present invention relates to a shaped body made of reactive foam, wherein at least one fiber (F) is located partially within the shaped body, ie is enclosed by the reactive foam. The two ends of the respective fiber (F) not surrounded by the reactive foam thus protrude from one side of the corresponding shaped body.
  • the reactive foam is produced by a foam molding process.
  • Another object of the present invention is a panel comprising at least one such shaped body and at least one further layer (S1). Further objects of the present invention are methods for producing the shaped bodies according to the invention from reactive foam or the panels according to the invention and their use, for example as a rotor blade in wind turbines.
  • WO 2006/125561 relates to a method for producing a reinforced cellular material, wherein in a first method step at least one hole is created in the cellular material extending from a first surface to a second surface of the cellular material. On the other side, the second surface of the cellular material, at least one fiber bundle is provided, this fiber bundle being pulled with a needle through the hole to the first side of the cellular material. However, before the needle grasps the fiber bundle, the needle is first pulled from the first side of the cellular material through the respective hole.
  • the fiber bundle is partly located within the cellular material, since it fills the corresponding hole, in part the corresponding fiber bundle protrudes on the respective sides from the first and second surface of the cellular material.
  • the method described in WO 2006/125561 can be used to produce sandwich-type components comprising a core of said cellular material and at least one fiber bundle. On the surfaces of this core, resin layers and fiber-reinforced resin layers may be applied to produce the actual sandwich-type component.
  • the cellular material for forming the core of the sandwich-type component polyvinyl chlorides or polyurethanes, for example, can be used.
  • a fiber bundle for example, carbon fibers, nylon fibers, glass fibers or polyester fibers in question.
  • WO 2006/125561 does not disclose that reactive foams produced by a foam molding process are used as the cellular material for producing a foam Kerns can be used in a sandwich-like component.
  • the sandwich-like components according to WO 2006/125561 are suitable for use in aircraft construction.
  • WO 201 1/012587 relates to another process for producing a core with integrated bridge fibers for panels of composite materials.
  • the core is made by partially or fully drawing through a bridle fiber provided on a surface of the respective cake by means of a needle through a so-called "cake" made of light material Foam, in particular be formed of a polyurethane foam.
  • any type of single or multiple threads and other yarns can be used as the fibers.
  • the cores thus produced may in turn be part of a panel of composite materials, wherein the core is surrounded on one or both sides by a resin matrix and combinations of resin matrices with fibers in a sandwich-like configuration.
  • WO 201 1/012587 does not disclose that reactive foams produced by a foam molding process can be used to produce the corresponding core material.
  • WO 2012/138445 relates to a method of making a composite core panel using a plurality of elongated strips of a low density cellular material. Between the respective strips a double-layered fiber mat is introduced which, by using resin, causes the individual strips to stick together to form the composite core panels.
  • the cellular material of low density forming the elongated strips is selected according to WO 2012/138445 from balsa wood, elastic foams or fiber-reinforced composite foams.
  • the double-layered fiber mats introduced between the individual strips may be, for example, a porous glass fiber mat.
  • the resin used as the adhesive may be, for example, a polyester, an epoxy or a phenolic resin or a thermally activated thermoplastic, for example polypropylene or PET.
  • WO 2012/138445 does not disclose that as a cellular material for the elongated strips, a reactive foam prepared by a foam molding process can also be used. Nor is it disclosed that single fibers or fiber bundles can be incorporated into the cellular material for reinforcement. According to WO 2012/138445 exclusively fiber mats are used for this purpose, which also represent a connecting member in the context of an adhesive bond of the individual strips by means of resin to obtain the core material.
  • GB-A-2 455 044 discloses a method for producing a multilayer composite article, wherein in a first method step a plurality of pellets of thermoplastic material and a blowing agent are provided.
  • the thermoplastic material is a mixture of polystyrene (PS) and polyphenylene oxide (PPO) containing at least 20 to 70 weight percent PPO.
  • PS polystyrene
  • PPO polyphenylene oxide
  • the pellets are expanded and welded in a third step in a mold to form a closed-cell foam of the thermoplastic material into a shaped body, wherein the closed-cell foam assumes the shape of the mold.
  • a layer of fiber-reinforced material is applied to the surface of the closed-cell foam, the attachment of the respective surfaces being carried out using an epoxy resin.
  • GB-A-2 455 044 does not disclose that a fibrous material can be incorporated into the core of the multilayer composite article.
  • a similar method or an analogous multilayer composite article (as in GB-A 2 455 044) is also disclosed in WO 2009/047483.
  • These multilayer composite articles are suitable, for example, for use as rotor blades (in wind turbines) or as boat hulls.
  • US Pat. No. 7,201,625 discloses a method for the production of foam products and the foam products as such, which can be used, for example, in sports as a surfboard.
  • the core of the foam product forms a particle foam, for example based on a polystyrene foam.
  • This particle foam is produced in a special form, wherein a plastic outer skin encloses the particle foam.
  • the plastic outer skin can be, for example, a polyethylene film.
  • US Pat. No. 7,201,625 does not disclose that fibers for reinforcing the material can be contained in the particle foam.
  • US-B 6,767,623 discloses sandwich panels comprising a core layer of polypropylene particle foam based on particles having a particle size in the range of 2 to 8 mm and a bulk density in the range of 10 to 100 g / l. Furthermore, the sandwich panels comprise two cover layers of fiber-reinforced polypropylene, wherein the individual cover layers are arranged around the core, that a sandwich is formed. Optionally, further layers may be included for decorative purposes in the sandwich panels.
  • the cover layers may contain glass fibers or other polymer fibers.
  • EP-A 2 420 531 discloses extruded foams based on a polymer such as polystyrene, in which at least one mineral filler with a particle size of ⁇ 10 ⁇ m and at least one nucleating agent are present. These extrusion foams are characterized by their improved rigidity. Furthermore, a corresponding extrusion process for producing such extruded foams based on polystyrene is described. The extrusion foams may be closed cell. However, EP-A 2 480 531 does not describe that the extrusion foams contain fibers.
  • WO 2005/056653 relates to particle foam moldings made of expandable polymer granules containing filler.
  • the particle foam moldings are obtainable by welding prefoamed foam particles of expandable, filler-containing, thermoplastic polymer granules, wherein the particle foam has a density in the range of 8 to 300 g / l.
  • the thermoplastic polymer granules are in particular a styrene polymer.
  • filler powdery inorganic substances, metal, chalk, aluminum hydroxide, calcium carbonate or alumina or spherical or fibrous inorganic substances such as glass beads, glass fibers or carbon fibers can be used.
  • US 3,030,256 describes laminated panels and a method for their production.
  • the panels include a core material into which fiber bundles are introduced and surface materials.
  • the core materials are foamed plastic and expanded plastic.
  • the fibers are located within a fiber region within the foam. A first fiber region protrudes from the first side of the molding, a second fiber region protrudes from the second side of the molding.
  • US 6,187,411 relates to reinforced sandwich panels comprising a foam core material having a fibrous layer on both sides and fibers which are pierced through the outer fibrous layers and the foam.
  • Foamed core materials are polyurethanes, phenols and isocyanates.
  • US 2010/0196652 relates to quasi-isotropic sandwich structures comprising a core material surrounded by fiber mats with glass fiber rovings pricking into the fiber mats and the core material.
  • foams various foams, such as polyurethane, polyisocyanurate, phenols, polystyrene, PEI, polyethylene, polypropylene and the like are described.
  • a disadvantage of the composite materials described in US Pat. No. 3,030,256, US Pat. No. 6,187,411 and US 2010/0196652 is that they frequently have a high resin uptake.
  • reactive foams there are a variety of different manufacturing processes, materials and resulting properties.
  • the object underlying the present invention is to provide new fiber-reinforced moldings or panels.
  • a molded body of reactive foam wherein at least one fiber (F) is located with a fiber region (FB2) within the molding and is enclosed by the reactive foam, while a fiber region (FB1) of the fiber (F) from a protruding first side of the molded body and a fiber portion (FB3) of the fiber (F) protrudes from a second side of the shaped body, wherein the reactive foam is produced by a foam molding process, wherein the fiber (F) at an angle ⁇ of 10 to 70 ° relative to Thickness direction (d) of the shaped body is introduced into the reactive foam and wherein the shaped body is obtainable by a process comprising the steps a) to f): a) optionally applying at least one layer (S2) on at least one side of the reactive foam, b) production from a hole per fiber (F) in the reactive foam and optionally the layer (S2), wherein the hole of a c) providing at least one fiber (F) on the second side of the
  • the subject of the present invention is also a shaped body of reactive foam in which at least one fiber (F) is located within the shaped body with a fiber region (FB2) and is enclosed by the reactive foam, while a fiber region (FB1) of the fiber (F) consists of a protrudes first side of the shaped body and a fiber region (FB3) of the fiber (F) protrudes from a second side of the shaped body, wherein the reactive foam is prepared by a foam molding process.
  • the reactive foam is obtainable by a foam molding process.
  • the moldings according to the invention are advantageously characterized by a low resin absorption and at the same time good interfacial bonding, wherein the low resin absorption is due in particular to the reactive foam produced by a foam molding process. This effect is of particular importance when the shaped bodies according to the invention are further processed into the panels according to the invention.
  • the fibers can advantageously be introduced first of all dry and / or by mechanical processes into the reactive foam.
  • the fibers or fiber bundles are not flush to the respective reactive foam surfaces, but deposited with supernatant and thus allow an improved connection or a direct connection with the corresponding cover layers in the panel according to the invention. This is the case in particular if, as cover layer, according to the invention at least one further layer (S1) is applied to the shaped bodies according to the invention with the formation of a panel.
  • two layers (S1) which may be the same or different, are applied.
  • two identical layers (S1) in particular two identical fiber-reinforced resin layers, are applied to opposite sides of the molded body according to the invention to form a panel according to the invention.
  • Such panels are also referred to as “sandwich materials", wherein the shaped body according to the invention can also be referred to as "core material”.
  • the panels of the invention are thus characterized by a low resin absorption in conjunction with a good peel strength and a good shear stiffness and a high shear modulus. Furthermore, high strength and stiffness properties are specifically adjusted by the choice of fiber types, their proportion and arrangement.
  • the effect of a low resin absorption is important because when using such panels (sandwich materials) often the goal is that the structural properties should be increased with the lowest possible weight.
  • the resin absorption of the shaped body (core material) contributes to the overall weight.
  • the resin absorption can be reduced, as a result of which weight and costs can be saved.
  • the closed surface of the reactive foam can be considered.
  • the reactive foam After the reactive foam is produced by a foam molding process, there is typically a sealed (closed) surface of high surface quality, characterized by minimal resin uptake and a density gradient from the core of the reactive foam towards the surface, the density being from the core of the reactive foam increases to its surface.
  • a reactive foam having a density gradient wherein the density increases from the core of the reactive foam towards its surface is also referred to as integral foam.
  • closed surface is understood to mean the following: The closed surface is evaluated by light or electron microscopic images defined as: (1 - area fraction of the opened foam cells) / total surface area> 30%, preferably> 50%, more preferably> 80%, in particular> 95%.
  • a further advantage of the shaped bodies or panels according to the invention is that due to the use of reactive foams or the production associated therewith, the attachment of integrated structures such as slots or holes on the surfaces of the shaped bodies as well as the further processing of the shaped bodies is relatively simple.
  • shaping steps such as thermoforming or machining integrate.
  • such structures are often used in draping curved structures (deep slits), improving workability by liquid resin processes such as vacuum infusion (holes), and accelerating the aforementioned processing (shallow slits) when using such moldings (core materials).
  • the introduced structures also preferably have a closed surface and thus a very low or even no resin absorption.
  • layers (S2) can be applied to the reactive foam during or after production. Such layers (S2) improve the overall cohesion of the reactive foam or the molding according to the invention.
  • the resin (cover) layer is applied by liquid injection or liquid infusion process, in which the fibers can be impregnated with resin during processing and the mechanical properties can be improved. In addition, this can be cost savings.
  • the shaped body comprises a reactive foam and at least one fiber (F).
  • the fiber (F) contained in the shaped body is a single fiber or a fiber bundle, preferably a fiber bundle.
  • fiber (F) are all known in the art materials that can form fibers.
  • the fiber (F) is an organic, inorganic, metallic, ceramic fiber or a combination preferably a polymeric fiber, basalt fiber, glass fiber, carbon fiber or natural fiber, more preferably a polyaramid fiber, glass fiber, basalt fiber or carbon fiber
  • a polymeric fiber is preferably a fiber of polyester, polyamide, polyaramid, polyethylene, polyurethane, polyvinyl chloride, polyimide and / or Polyamide-imide
  • a natural fiber is preferably a fiber of sisal, hemp, flax, bamboo, coconut and / or jute.
  • fiber bundles are used.
  • the fiber bundles are composed of several individual fibers (filaments).
  • the number of single fibers per bundle is at least 10, preferably 100 to 100,000, more preferably 300 to 10,000 in glass fibers and 1,000 to 50,000 in carbon fibers, and more preferably 500 to 5,000 in glass fibers and 2,000 to 20,000 in carbon fibers.
  • the at least one fiber (F) with a fiber region (FB2) is located inside the molding and is enclosed by the reactive foam, while a fiber region (FB1) of the fiber (F) protrudes from a first side of the molding and a fiber region (FB3) the fiber (F) protrudes from a second side of the shaped body.
  • the fiber region (FB1), the fiber region (FB2) and the fiber region (FB3) can each make up an arbitrary fraction of the total length of the fiber (F).
  • the fiber region (FB1) and the fiber region (FB3) each independently form 1 to 45%, preferably 2 to 40% and more preferably 5 to 30%, and the fiber region (FB2) 10 to 98%, preferably 20 to 96%, more preferably 40 to 90% of the total length of the fiber (F).
  • the first side of the shaped body, from which the fiber region (FB1) of the fiber (F) protrudes faces the second side of the shaped body, from which the fiber region (FB3) of the fiber (F) protrudes.
  • the fiber (F) is introduced at an angle ⁇ of 10 to 70 ° relative to the thickness direction (d) of the molding or to the orthogonal (the surface) of the first side (2) of the molding in the molding.
  • the fiber (F) is preferably introduced into the reactive foam at an angle ⁇ of 30 to 60 °, preferably 30 to 50 °, more preferably 30 to 45 °, in particular 45 °, relative to the thickness direction (d) of the shaped body.
  • angle ⁇ can assume any values from 0 to 90 °.
  • the fiber (F) is then at an angle ⁇ of 0 to 60 °, preferably from 0 to 50 °, more preferably from 0 to 15 ° or from 10 to 70 °, preferably from 30 to 60 °, more preferably from 30 to 50 °, even more preferably from 30 to 45 °, in particular from 45 °, introduced relative to the thickness direction (d) of the molding in the reactive foam.
  • At least two fibers (F) in two different angles ⁇ , ai and a 2 introduced, wherein the first angle ⁇ - ⁇ preferably in the range of 0 ° to 15 ° and the second angle a 2 preferably in the range of Is 30 to 50 °, more preferably ai is in the range of 0 ° to 5 ° and a 2 in the range of 40 to 50 °.
  • All fibers (F) are preferred at an angle ⁇ in the range of 10 to 70 °, preferably 30 to 60 °, more preferably in the range of 30 to 50 °, even more preferably 30 to 45 °, most preferably 45 ° relative to the thickness direction (d) of the molding introduced into the reactive foam.
  • a shaped body according to the invention contains a multiplicity of fibers (F), preferably as fiber bundles, and / or comprises more than 10 fibers (F) or fiber bundles per m 2 , preferably more than 1000 per m 2 , particularly preferably 4000 to 40 000 per m 2 .
  • all the fibers (F) in the molding according to the invention have the same angle ⁇ or at least approximately the same angle (deviation of at most + / - 5 °, preferably + / - 2 °, more preferably + / - 1 °).
  • All fibers (F) may be present parallel to each other in the molding.
  • two or more fibers (F) may be present at an angle ⁇ to one another in the shaped body.
  • the angle ⁇ is the angle between the vertical projection of a first fiber (F1) onto the surface of the first side of the shaped body and the perpendicular projection of a second fiber (F2) onto the surface of the shaped body, both fibers are introduced into the molding.
  • n is in the range of 2 to 6, more preferably in the range of 2 to 4.
  • the angle ⁇ is 90 °, 120 ° or 180 °.
  • the angle ⁇ is in the range of 80 to 100 °, in the range of 1 10 to 130 ° or in the range of 170 to 190 °.
  • more than two fibers (F) are introduced at an angle ⁇ to one another, for example three or four fibers (F). These three or four fibers (F) can each be to the two adjacent fibers two different angles ß, ß- ⁇ and ß 2 , have. Preferably, all fibers (F) to the two adjacent fibers (F) at the same angle.
  • the angle ⁇ is 90 °
  • the angle ⁇ i between the first fiber (F1) and the second fiber (F2) is 90 °
  • the angle ⁇ 2 between the second fiber (F2) and third fiber (F3) is 90 °
  • the angle ⁇ 3 between the third fiber (F3) and the fourth fiber (F4) is 90 °
  • the angle ⁇ 4 between the fourth fiber (F4) and the first fiber (F1) is also 90 °.
  • the angle ⁇ between the first fiber (F1) (reference) and the second (F2), third (F3) and fourth fiber (F4) is then 90 ° clockwise, 180 ° and 270 °. Analogous considerations apply to the other possible angles.
  • the first fiber (F1) then has a first direction
  • the second fiber (F2) which is arranged at an angle ß to the first fiber (F1), has a second direction.
  • a similar number of fibers Preferably, in the first direction and the second direction, a similar number of fibers.
  • similar is meant herein that the difference between the number of fibers in each direction relative to the other direction is ⁇ 30%, more preferably ⁇ 10%, and most preferably ⁇ 2%.
  • the fibers or fiber bundles can be introduced in irregular or regular patterns. Preference is given to the introduction of fibers or fiber bundles in regular patterns.
  • regular patterns are understood to mean that all fibers are aligned parallel to one another and that at least one fiber or fiber bundle has the same distance (a) to all directly adjacent fibers or fiber bundles all the directly adjacent fibers or fiber bundles at the same distance.
  • the first fibers (F1) which are parallel to one another, preferably have a regular pattern with a first spacing (a-1) and the second fibers (F2) which are parallel to each other and are at an angle ⁇ to the first fibers (F1), preferably a regular pattern having a second distance (a 2 ).
  • the surface of at least one side of the shaped body has at least one recess, preferably the recess is a slot or a hole, more preferably at least one recess on the surface of at least one side of the Formed body after the implementation of step IV) of the foam molding process, and / or ii) the total surface area of the shaped body to more than 30%, preferably more than 50%, more preferably more than 80%, in particular more than 95 %, closed.
  • FIG. 1 shows a schematic representation of a preferred embodiment of the shaped body of reactive foam (1) according to the invention in a perspective view.
  • (2) represents (the surface) of a first side of the molding
  • (3) represents a second side of the corresponding molding.
  • the first side (2) of the shaped body lies opposite the second side (3) of this shaped body.
  • the fiber (F) is represented by (4).
  • One end of this fiber (4a) and thus the fiber portion (FB1) protrude from the first side (2) of the shaped body, while the other end (4b) of the fiber, which represents the fiber portion (FB3), from the second side (3 ) protrudes the molding.
  • the middle fiber region (FB2) is located within the molding and is thus enclosed by the reactive foam.
  • the fiber (4) which is for example a single fiber or a fiber bundle, preferably a fiber bundle, is at an angle ⁇ relative to the thickness direction (d) of the shaped body or to the orthogonal (the surface) of the first side (FIG. 2) of the molding.
  • the angle ⁇ is 10 to 70 °, preferably 30 to 60 °, particularly preferably 30 to 50 °, especially 30 to 45 °, in particular 45 °.
  • F single fiber
  • FIG. 3 shows, by way of example, a schematic representation of part of the various angles.
  • the shaped body of reactive foam (1) shown in FIG. 3 contains a first fiber (41) and a second fiber (42).
  • the first fiber (41) forms a first angle ⁇ ( ⁇ 1) relative to the orthogonal (O) of the surface of the first side (2) of the shaped body.
  • the second fiber (42) forms a second angle ⁇ ( ⁇ 2) relative to the orthogonal (O) of the surface of the first side (2).
  • the perpendicular projection of the first fiber (41) onto the first side (2) of the shaped body (41 p) forms the angle ⁇ with the perpendicular projection of the second fiber (42) onto the first side (2) of the shaped body (42 p).
  • the reactive foam contained in the molded body is produced by a foam molding process.
  • the foam molding process comprises the following steps I) to IV).
  • step IV) demolding of the expanded foam obtained in step II I) from the forming tool to obtain the reactive foam.
  • first component (K1) and second component (K2) contained in the reactive mixture provided in step I) all the first components (K1) and second components (K2) which are capable of reacting with each other are suitable. Such components are known in the art as such.
  • isocyanates are suitable. Isocyanates as such are known to the person skilled in the art. In the context of the present invention, isocyanates are understood as meaning all aliphatic, cycloaliphatic and aromatic di- and / or polyisocyanates. Aromatic di- and / or polyisocyanates are preferred. Particularly preferred as the first component (K1) are toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polymeric diphenylmethane diisocyanates (PMDI) and mixtures thereof. Especially preferred are mixtures of diphenylmethane diisocyanate (MDI) and polymeric diphenylmethane diisocyanates (PMDI) as the first component (K1).
  • TDI toluene diisocyanate
  • MDI diphenylmethane diisocyanate
  • PMDI polymeric diphenylmethane diisocyanates
  • K1 isocyan
  • isocyanates are used as the first component (K1), these may be modified in whole or in part with uretdione, carbamate, isocyanurate, carbodiimide, allophanate and / or urethane groups. Preferably, they are modified with urethane groups. Such isocyanates are known in the art as such.
  • isocyanates are prepolymers and mixtures of the isocyanates and prepolymers described above.
  • the prepolymers are prepared from the isocyanates described above and the polyethers, polyesters or mixtures thereof described below.
  • Isocyanates suitable as first component (K1) preferably have an isocyanate index in the range from 100 to 400, particularly preferably in the range from 100 to 300, particularly preferably in the range from 100 to 200.
  • the isocyanate index is understood as meaning the stoichiometric ratio of isocyanate groups to isocyanate-reactive groups, 20 multiplied by 100.
  • Isocyanate-reactive groups are understood to mean all isocyanate-reactive groups present in the reactive mixture, including, if appropriate, chemical blowing agents and compounds containing epoxide groups, but not the isocyanate group itself.
  • the second component (K2) used is preferably at least one compound containing isocyanate-reactive groups. Such compounds are known to the person skilled in the art.
  • all compounds which have at least two isocyanate-reactive groups such as OH, SH, N H and / or CH-azide groups, can be used as compound with isocyanate-reactive groups.
  • Preferred as a second component (K2) is a compound having isocyanate-reactive groups which is selected from the group consisting of
  • polyether polyols 35 polyether polyols, polyester polyols and polyamines, wherein the at least one compound having isocyanate-reactive groups having a functionality of 2 to 8 and wherein, when the second component (K2) is selected from polyether polyols and polyester polyols containing at least one compound with isocyanate-reactive groups an average hydroxyl number of
  • Polyether polyols as such are known to the person skilled in the art and can be prepared by known processes, for example by anionic polymerization of alkylene oxides with the addition of at least one starter molecule which preferably contains 2 to 6 bonded reactive hydrogen atoms, in the presence of catalysts.
  • catalysts alkali metal hydroxides such as sodium or potassium hydroxide or alkali metal such as sodium, sodium or potassium or potassium are used.
  • the catalysts used are, for example, Lewis acids such as ammonium pentachloride, boron trifluoride etherate or bleaching earth.
  • DMC catalysts double metal cyanide compounds
  • amine-based catalysts double metal cyanide compounds
  • alkylene oxides one or more compounds having two to four carbon atoms in the alkylene radical such as ethylene oxide, Tetra h yd rofu ran, 1, 2-propylene oxide, 1, 3-propylene oxide, 1, 2-butylene oxide, 2,3-butylene oxide and mixtures from it, used. Preference is given to using ethylene oxide and / or 1,2-propylene oxide.
  • starter molecules are ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerol, trimethylolpropane, pentaerythritol, sugar derivatives such as sucrose, hexitol derivatives such as sorbitol, methylamine, ethylamine, isopropylamine, butylamine, benzylamine, aniline, toluidine, toluenediamine, naphthylamine, ethylenediamine, diethylenetriamine, 4 4'-methylenedianiline, 1, 3-propanediamine, 1, 6-hexanediamine, ethanolamine, diethanolamine, triethanolamine and other known to those skilled di- or polyhydric alcohols or mono- or polyhydric amines into consideration.
  • polyester polyols are all polyester polyols known to those skilled in the art.
  • suitable polyester polyols may be prepared by condensing polyhydric alcohols of two to twelve carbons such as ethylene glycol, diethylene glycol, butanediol, trimethylolpropane, glycerol or pentaerythritol with polyfunctional carboxylic acids having two to twelve carbon atoms, for example, succinic, glutaric, adipic, suberic, azelaic, sebacic, decanedicarboxylic , Maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, the isomers of naphthalenedicarboxylic acids, the anhydrides of said acids, and mixtures thereof.
  • aromatic diacids such as phthalic acid, isophthalic acid and / or terephthalic acid and their anhydrides as the acid component and ethylene glycol, diethylene glycol, 1,4-butanediol and / or glycerol as the alcohol component.
  • polyfunctional carboxylic acids and corresponding monomeric esters such as dimethyl terephthalate or polymeric esters such as polyethylene terephthalate can be used to prepare the polyester.
  • Suitable polyamines are all polyamines known to the person skilled in the art. Suitable polyamines are both aliphatic polyamines and aromatic polyamines. Preference is given to aliphatic polyamines, which are also referred to as polyalkylenepolyamines in the context of the present invention.
  • polyalkylenepolyamine is understood as meaning aliphatic amines containing at least three amino groups (primary, secondary or tertiary) .
  • Polyethylene polyethylenes are particularly preferably polyethylenimines Homopolymers and copolymers understood which have the groupings -CH 2 -CH 2 -NH- and contain at least three amino groups.
  • the first component (K1) and the second component (K2) can react with each other. These reactions are known to those skilled in the art.
  • first component (K1) with the second component (K2) for example, form polyurethanes, polyisocyanurates or polyureas, preferably form polyisocyanates or polyurethanes, most preferably form polyurethanes.
  • polyurethanes for example, polyurethanes, polyisocyanurates or polyureas, preferably form polyisocyanates or polyurethanes, most preferably form polyurethanes.
  • polyurethanes are formed when isocyanates are used as the first component (K1) and polyether polyols as the second component (K2).
  • Polyisocyanurates are formed in the use of isocyanates as the first component (K1) and polyester polyols as the second component (K2).
  • Polyureas are obtained by the reaction of isocyanates as the first component (K1) and polyamines as the second component (K2).
  • polyurethanes may also contain, for example, isocyanurate units, allophanate units, urea units, carbodiimide units, biuret units, uretonimine units and optionally further units which may form as addition reaction of isocyanates as first component (K1).
  • polyisocyanurates may, for example, also urethane units, allophanate units, urea units, carbodiimide units, biuret units, uretonimine units and optionally further units which may be in addition reactions of isocyanates as the first component (K1) can form included.
  • polyureas for example, can also contain isocyanurate units, allophanate units, urethane units, carbodiimide units, biuret units, uretonimine units and optionally further units which can form as addition reaction of isocyanates as first component (K1).
  • step I) The provision of the reactive mixture in step I) can be carried out by all methods known to the person skilled in the art.
  • the first component (K1) and the second component (K2) as well as the optional further components and / or catalysts and / or further additives contained in the reactive mixture are usually mixed.
  • the mixing takes place for example at a temperature in the range of 15 to 130 ° C, preferably in the range of 15 to 90 ° C, particularly preferably in the range of 25 to 55 ° C.
  • the mixing can be carried out by all methods known to the person skilled in the art, for example mechanically by means of a stirrer or a stirring screw or under high pressure in a countercurrent injection method.
  • the reactive mixture provided in step I) may also contain further components.
  • Other components include physical and / or chemical blowing agents.
  • chemical blowing agents are understood to mean blowing agents which are initially present in solid or liquid form in the reactive mixture and then by chemical reaction with the components (K1) and / or (K2), and optionally with others in the reactive one Mix containing components react, forming gaseous products, which then serve as the actual propellant.
  • blowing agents are understood to mean blowing agents which, if appropriate under pressure, are dissolved or emulsified in the reactive mixture and evaporate under the conditions in which the reactive mixture reacts.
  • Suitable chemical and physical blowing agents are known to those skilled in the art.
  • the chemical blowing agents include, for example, water and carboxylic acids, especially formic acid.
  • the physical blowing agents include, for example, hydrocarbons, in particular (cyclo) aliphatic hydrocarbons, halogenated hydrocarbons such as perfluorinated alkanes, pentafluorohexane, chlorofluorocarbons, Etheresterketone and acetals, and inorganic and organic compounds that release nitrogen when heated.
  • hydrocarbons in particular (cyclo) aliphatic hydrocarbons
  • halogenated hydrocarbons such as perfluorinated alkanes, pentafluorohexane, chlorofluorocarbons, Etheresterketone and acetals
  • inorganic and organic compounds that release nitrogen when heated.
  • Preferred (cyclo) aliphatic hydrocarbons having 4 to 8 carbon atoms are, for example, n-pentane, iso-pentane and cyclopentane.
  • the propellant of the reactive mixture is selected from the group consisting of n-pentane, iso-pentane, cyclopentane, 1,1,1,3,3-pentafluorobutane, 1,1,1,3,3-pentafluoropropane, 1,1 , 1, 2,3,3,3-heptafluoropropane, water, formic acid and hydrofluoroolefins, such as 1,1,1,4,4,4-hexafluoro-2-butenes and 1-chloro-3,3,3-trifluoro-propenes , Further preferably, the propellant contains water, more preferably the propellant is water.
  • the reactive mixture may contain catalysts.
  • catalysts it is possible to use all compounds which accelerate the reaction of the first component (K1) with the second component (K2). Such compounds are known and described for example in "Kunststoffhandbuch Volume 7, polyurethane, Karl Hanser Verlag, 3rd edition 1993, chapter 3.4.1".
  • the reactive mixture provided in step I) may contain further additives.
  • additives are known in the art as such. Additives are, for example, stabilizers, surface-active substances, flame retardants and chain extenders.
  • Stabilizers are also referred to as foam stabilizers.
  • stabilizers are understood to be substances which promote the formation of a regular cell structure during foam formation.
  • suitable Stabilizers are, for example, silicone-containing foam stabilizers such as siloxane-oxalkylene copolymers and other organopolysiloxanes, and also alkoxylation products of fatty alcohols, oxoalcohols, fatty amines, alkylphenols, dialkylphenols, alkylcresols, alkylresorcinol, naphthol, alkylnaphthol, naphthylamine, aniline, alkylaniline, toluidine, bisphenol A, alkylated bisphenol A , Polyvinyl alcohol and other alkoxylation of condensation products of formaldehyde and alkylphenols, formaldehyde and dialkylphenols, formaldehyde and alkylcresols, formaldehyde and alky
  • Surface-active substances are also referred to as surface-active substances.
  • Surface-active substances are compounds which serve to assist the homogenization of the starting materials and, if appropriate, are also suitable for regulating the cell structure of the plastics. These include, for example, emulsifiers such as sodium salts of castor oil sulfates or of fatty acids and salts of fatty acids with amines, e.g. diethylamine oleate, diethanolamine stearate, diethanolamine ricinoleic acid, salts of sulfonic acids, e.g. Alkali or ammonium salts of dodecylbenzene disulfonic acid, dinaphthylmethanedisulfonic acid and ricinoleic acid.
  • emulsifiers such as sodium salts of castor oil sulfates or of fatty acids and salts of fatty acids with amines, e.g. diethylamine oleate, diethanolamine
  • flame retardants for example, organic phosphoric acid and / or phosphonic acid esters can be used. Preference is given to using non-reactive compounds over isocyanate groups. Chlorine-containing phosphoric acid esters are also among the preferred compounds. Suitable flame retardants are, for example, tris (2-chloropropyl) phosphate, triethyl phosphate, diphenyl cresyl phosphate, diethyl ethane phosphinate, tricresyl phosphate, tris (2-chloroethyl) phosphate, tris (1,3-dichloropropyl) phosphate, tris- (2,3-) dibromopropyl) phosphate, tetrakis- (2-chloroethyl) ethylenediphosphate, dimethylmethanephosphonate, diethanolaminomethylphosphonic acid diethyl ester and commercially available halogenated flame retardant polyols.
  • bromine-containing flame retardants can be used.
  • the bromine-containing flame retardants used are preferably compounds which are reactive toward the isocyanate group.
  • Such compounds are, for example, esters of tetrabromophthalic acid with aliphatic diols and alkoxylation products of dibromobutenediol.
  • Compounds derived from the brominated, OH group-containing neopentyl compounds may also be used.
  • inorganic or organic flame retardants such as red phosphorus, alumina hydrate, antimony trioxide, arsenic oxide, ammonium polyphosphate and calcium sulfate, expandable graphite or cyanuric acid derivatives such as melamine or mixtures of two flame retardants such as ammonium polyphosphates and melamine and optionally corn starch or ammonium polyphosphate, melamine and expandable graphite and / or optionally aromatic polyesters are used to flame-retard the polyisocyanate polyaddition products.
  • Chain extenders are understood to mean bifunctional compounds. Such compounds are known in the art as such.
  • Suitable chain extenders are, for example, aliphatic, cycloaliphatic and / or aromatic diols having two to fourteen, preferably two to ten carbon atoms, such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-pentanediol, 1,3-pentanediol, 1, 10-decanediol, 1,2-dihydroxycyclohexane, 1,3-dihydroxycyclohexane, 1,4-dihydroxycyclohexane, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, 1,6-hexanediol and bis (2-hydroxyethyl ) hydroquinone.
  • step I I) the reactive mixture provided in step I) is injected into a forming tool. Processes for this are known to the person skilled in the art. Usually, the injection of the reactive mixture into the forming tool is discontinuous.
  • the injection of the reactive mixture can be carried out, for example, under elevated pressure.
  • the conversion of the reactive mixture, based on the isocyanate groups, during step I I) is preferably less than 90%.
  • the amount of reactive mixture injected into the forming tool in step I) is such that the reactive foam obtained in step IV) has the desired overall density and foam structure. If the reactive foam is an integral foam, it is preferred that the degree of compaction is in the range of from 1.05 to 4, preferably in the range of 1.1 to 3.
  • the degree of compaction is the ratio of the final density of the reactive foam produced by the foam molding process to the density of the free-foamed reactive foam.
  • the forming tool may comprise carrier and / or release layers. Such carrier and / or separating layers are known to the person skilled in the art.
  • the carrier and / or release layer is a layer (S2).
  • S2 the carrier and / or release layer.
  • the embodiments and preferences for the layer (S2) described below apply to this carrier and / or release layer.
  • step II I) the reactive mixture is expanded. The expansion of the reactive mixture takes place by the reaction of the first component (K1) with the second component (K2). Such reactions are known in the art. In addition, the expansion may be promoted by the chemical and / or physical blowing agent optionally contained in the reactive mixture.
  • the expansion of the reactive mixture may be initiated, for example, by the catalyst optionally contained in the reactive mixture.
  • the reactive mixture is expanded to the extent that the resulting expanded foam completely fills the molding tool. Contains the forming tool carrier and / or release layers, so the expanded foam connects to these.
  • the mold temperature during step I II) is usually in the range of 20 to 200 ° C, preferably in the range of 30 to 140 ° C, particularly preferably in the range of 30 to 80 ° C.
  • the mold temperature during all steps I) to IV) of the foam molding process in the range of 20 to 200 ° C, preferably in the range of 30 to 140 ° C, particularly preferably in the range of 30 to 80 ° C.
  • step IV the expanded foam obtained in step I II) is removed from the forming tool to obtain the reactive foam.
  • the foam molding process for producing the reactive foam is preferably carried out as a one-shot process, particularly preferably using the low-pressure technique or the high-pressure technique. In this case, usually closed and optionally tempered shaping tools are used.
  • the one-shot process for polyurethanes is described, for example, by Piechota and Rschreib in "Integralschaumstoff", Carl Hanser Verlag, Kunststoff, Vienna, 1975, or in the "Kunststoffhandbuch", Volume 7, Polyurethane, 3rd edition, 1993, Chapter 7.
  • a one-shot method is known to those skilled in the art. In the one-shot method, steps I) and II) are carried out directly one after the other or simultaneously.
  • the first component (K1) and the second component (K2) present in the reactive mixture and, if appropriate, the further components, the catalyst and the further additives are mixed with one another during the injection into the shaping tool, for example in US Pat a static or dynamic mixer.
  • the resulting reactive foam can be processed optionally after cutting and / or thermally in connection with step IV). Methods for this purpose are known to those skilled in the art. Preferably, after removal from the mold in accordance with step IV), no cutting and / or thermal processing of the reactive foam takes place.
  • the length of the reactive foam thus obtained is referred to as the x-direction, the width as the y-direction and the thickness as the z-direction.
  • the reactive foam of the invention may have any size.
  • the reactive foam produced according to the invention has a thickness (z-direction) in the range of 4 to 200 mm, preferably in the range of 5 to 60 mm, a length (x-direction) of at least 200 mm, preferably of at least 400 mm and a width (y-direction) of at least 200 mm, preferably of at least 400 mm.
  • the reactive foam usually has a length (x-direction) of not more than 4000 mm, preferably of not more than 2500 mm, and / or a width (y-direction) of not more than 4000 mm, preferably of not more than 2500 mm.
  • the reactive foam is preferably based on a polyurethane, a polyurea or a polyisocyanurate. Particularly preferred is the reactive foam based on a polyurethane.
  • the reactive foam based on a polyurethane, a polyurea or a polyisocyanurate it means in the present invention that the reactive foam in addition to the polyurethane, polyurea or polyisocyanurate may contain other polymers, for example as a blend of the polyurethane, the polyurea or the polyisocyanurate and another polymer. Processes for the preparation of these blends are known to the person skilled in the art. If the reactive foam based on a polyurethane, it is also preferred that it is a polyurethane foam, in particular a Semi-rigid polyurethane foam, a flexible polyurethane foam or a polyurethane rigid foam.
  • the reactive foam is based on a polyurethane, a polyurea or a polyisocyanurate, which is prepared in each case by a foam molding process comprising the abovementioned steps I) to IV), and in which the reactive Mixture as the first component (K1) at least one polyisocyanate and as a second component (K2) at least one compound containing isocyanate-reactive groups and as further component at least one blowing agent.
  • the reactive foam based on a polyurethane prepared by a foam molding process comprising the above-mentioned steps I) to IV) and wherein the first component (K1) is selected from diphenylmethyl diisocyanate and polymeric diphenylmethane diisocyanate and the second component (K2 ) is at least one compound having isocyanate-reactive groups which is selected from the group consisting of polyether polyols, polyester polyols and polyamines, wherein the at least one compound having isocyanate-reactive groups has a functionality of 2 to 8 and wherein when the second component ( K2) is selected from polyether polyols and polyester polyols having at least one compound having isocyanate-reactive groups an average hydroxyl number of 12 to 1200 mg KOH / g and the reactive mixture comprises a further component containing at least one propellant containing water.
  • the first component (K1) is selected from diphenylmethyl diisocyanate and polymeric diphenylmethane diis
  • the reactive foam usually has a glass transition temperature of at least 80 ° C., preferably of at least 110 ° C. and more preferably of at least 130 ° C., determined by differential scanning calorimetry (DTA).
  • the glass transition temperature of the reactive foam is generally not more than 400 ° C., preferably not more than 300 ° C., in particular not more than 200 ° C., determined by means of differential thermal analysis (DTA).
  • the subject of the present invention is also a panel comprising at least one shaped body according to the invention and at least one layer (S1).
  • a “panel” may also be referred to in the art as “sandwich”, “sandwich material”, “laminate” and / or “composite article”.
  • the panel has two layers (S1), and the two layers (S1) are each attached to one side of the shaped body opposite to the other side in the molded body.
  • the layer (S1) comprises at least one resin, preferably the resin is a reactive thermosetting or thermoplastic resin, more preferably the resin is based on epoxides, acrylates, polyurethanes, polyamides, polyesters, unsaturated polyesters, vinyl esters or mixtures thereof, in particular the resin is an amine-curing epoxy resin, a latent curing epoxy resin, an anhydride-curing epoxy resin or a polyurethane of isocyanates and polyols.
  • resin systems are known to the person skilled in the art, for example from Penczek et al. (Advances in Polymer Science, 184, pp. 1-95, 2005), Pham et al. (Ullmann's Encyclopedia of Industrial Chemistry, Vol. 13, 2012), Fahnler (Polyamides, Plastics Handbook 3/4, 1998) and Younes (W012134878 A2).
  • a panel in which i) the fiber region (FB1) of the fiber (F) is partially or completely, preferably completely, in contact with the first layer (S1), and / or ii) the fiber region (FB3) Fiber (F) is partially or completely, preferably completely, in contact with the second layer (S1), and / or iii) the panel has at least one layer (S2) between at least one side of the shaped body and at least one layer (S1),
  • the layer (S2) of sheet-like fiber materials or polymeric films more preferably of porous sheet-like fiber materials or porous polymeric films, particularly preferably of paper, glass fibers or carbon fibers in
  • Porosity is the ratio (dimensionless) of void volume (pore volume) to the total volume of a reactive foam. It is determined for example by image analysis of microscopic images by the void or pore volume is divided by the total volume.
  • the total porosity of a substance is made up of the sum of the voids that communicate with each other and the environment (open porosity) and the non-interconnected voids (closed porosity). Preference is given to layers (S2) which have a high open porosity.
  • the at least one layer (S1) additionally comprises at least one fibrous material, i) the fibrous material comprising fibers in the form of one or more layers of cut fibers, nonwovens, loops, knits and / or fabrics, preferably in
  • the fibrous material comprises fibers of organic, inorganic, metallic or ceramic fibers , preferably polymeric fibers, basalt fibers, glass fibers, carbon fibers or natural fibers, particularly preferably glass fibers or carbon fibers.
  • the natural fibers and the polymeric fibers apply the previously described embodiments.
  • a layer (S1) which additionally contains at least one fibrous material is also referred to as a fiber-reinforced layer, in particular as a fiber-reinforced resin layer, if the layer (S1) comprises a resin.
  • FIG. 2 shows another preferred embodiment of the present invention.
  • an inventive panel (7) is shown, which comprises a molded body (1) according to the invention, as shown for example in the context of the embodiment of FIG.
  • the reference numerals in other abbreviations in Figures 1 and 2 have the same meaning.
  • the panel according to the invention comprises two layers (S1), which are represented by (5) and (6).
  • the two layers (5) and (6) are thus located on mutually opposite sides of the shaped body (1).
  • the two layers (5) and (6) are preferably resin layers or fiber-reinforced resin layers.
  • the two ends of the fiber (4) are enclosed by the respective layer (5) or (6).
  • one or more further layers may be present between the shaped body (1) and the first layer (5) and / or between the shaped body (1) and the second layer (6).
  • a single fiber (F) is represented by (4).
  • a panel is preferred in which at least one of the following alternatives is fulfilled: i) the molded body contained in the panel contains at least one side which has not been mechanically and / or thermally processed, and / or ii) comprises the molded body contained in the panel at least one layer (S2) which was applied as a carrier film to the reactive foam in the foam-forming process comprising steps I) to V) in step II), and / or iii) the at least one layer (S1) comprises a resin and the reactive foam of the shaped body has a resin absorption of less than 1000 g / m 2 , preferably less than 500 g / m 2 and particularly preferably less than 100 g / m 2 , and / or iv) the panel has a peel strength of more than 200 J / m 2 , preferably of more than 500 J / m 2 , more preferably of more than 2000 J / m 2 , and / or v) the reactive foam of the molding contained in the panel has
  • the molded body contained in the panel has a specific shear strength measured in parallel to the at least a layer (S1) of at least
  • the molding contained in the panel has in Panel a shear modulus measured parallel to the at least one layer (S1) of at least 0.2 MPa / (kg / m 3 ), preferably of at least 0.6 MPa / (kg / m 3 ), more preferably of at least 1, 0 MPa / (kg / m 3 ), on.
  • the specific shear strength and the shear modulus are determined according to DI N 53294 (as of 1982) and the density according to ISO 845 (as of 2007).
  • the shear modulus of the molding according to alternative vi) refers to the shear modulus of the molding without the at least one layer (S1). Only the measurement takes place parallel to the side at which the at least one layer (S1) is applied in the panel.
  • the peel strength of the panel is determined with single cantilever beam (SCB) samples.
  • the thickness of the moldings is 20 mm, the layers (S1) each consist of about 2 mm thick quasi-isotropic glass fiber reinforced epoxy resin.
  • the panels are then tested in a Zwick Z050 tensile testing machine at a speed of 5 mm / min, loading and unloading the panel three to four times.
  • the crack growth or the increase in each load cycle (Aa) is determined optically.
  • the crack growth energy (AU) is determined from the force-displacement curve. From this, the fracture toughness or peel strength is determined as
  • the reactive foam and glass gels are used in addition to the resin systems used, the reactive foam and glass gels: nylon vacuum film, vacuum sealing tape, nylon flow aid, polyolefin release film, polyester tear off fabric and PTFE membrane film and polyester absorbent nonwoven.
  • Panels also referred to below as sandwich materials, are produced from the moldings by applying fiber-reinforced cover layers by means of vacuum infusion.
  • At the top and bottom of the (fiber-reinforced) foams are each two layers of Quadrax Glasgelege (Roving: E-Glass SE1500, OCV, textile: Saertex, isotropic laminate [0 -45 90 ° 45 °], each 1200 g / m 2 ) applied.
  • a release film is inserted between the molded body, hereinafter also referred to as core material, and the glass scrim, in contrast to the standard production of the panels.
  • core material hereinafter also referred to as core material
  • the glass scrim On the glass shelves the tear-off fabric and the flow aids are attached on both sides.
  • the assembly is then fitted with sprues for the resin system and ports for evacuation. Finally, a vacuum film is applied over the entire structure, sealed with sealing tape and evacuated the entire structure.
  • the structure is prepared on an electrically heated table with a glass surface.
  • the resin system used is amine-curing epoxy (resin: BASF Baxxores 5 5400, hardener: BASF Baxxodur 5440, mixing ratio and further processing according to data sheet).
  • the resin is evacuated for 10 minutes at up to 20 mbar.
  • a resin temperature of 23 + / - 2 ° C infusion takes place on the pre-tempered structure (table temperature: 35 ° C).
  • temperature ramp of 0.3 K / min from 35 ° C to 75 ° C and isothermal0 curing at 75 ° C for 6 h panels can be made, which consist of the reactive foams and glass fiber reinforced cover layers.
  • the moldings are measured according to ISO 845 (as of October 2009) in order to obtain the density of the molded body.
  • the processed panels are trimmed to eliminate excess resin build-up in the peripheral areas by non-conforming vacuum foil.
  • the cover layers are removed and the moldings contained are measured again by ISO 845.
  • the difference between the densities results in the absolute resin absorption.
  • the corresponding resin absorption results in kg / m 2 .
  • the present invention furthermore relates to a process for producing the shaped body according to the invention, wherein at least one fiber (F) is partially introduced into the reactive foam, whereby the fiber (F) with the fiber region (FB2) is located inside the shaped body and enclosed by the reactive foam is, while the fiber region (FB1) of the fiber (F) protrudes from a first side of the shaped body and the fiber region (FB3) of the fiber (F) protrudes from a second side of the shaped body.
  • the partial introduction of the at least one fiber (F) into the reactive foam by sewing using a needle preferably the partial introduction of steps a) to f): 0 a) optionally applying at least one Layer (S2) on at least one side of the reactive foam, b) producing one hole per fiber (F) in the reactive foam and optionally in the layer (S2), the hole extending from a first side to a second side of the reactive foam and optionally through the layer (S2), c) providing at least one fiber (F) on the second side of the reactive foam, d) passing a needle from the first side of the reactive foam through the hole to the second side of the reactive foam and optionally passing the needle through the layer (S2), e) affixing at least
  • Layer (S2) protrudes and the fiber region (FB3) of the fiber (F) protrudes from a second side of the molding, more preferably, the steps b) and d) are carried out simultaneously.
  • step a) The application of at least one layer (S2) in step a) can be carried out, for example, as described above during step II) of the foam molding process.
  • steps b) and d) are carried out simultaneously.
  • the hole is created from the first side to the second side of the reactive foam by passing a needle from the first side of the reactive foam to the second side of the reactive foam.
  • the introduction of the at least one fiber (F) may comprise, for example, the following steps: a) optionally applying a layer (S2) to at least one side of the reactive foam, b) providing at least one fiber (F) on the second side of the reactive foam; c) producing one hole per fiber (F) in the reactive foam and optionally in the layer (S2), the hole being from the first side to a second one Side of the reactive foam and optionally through the layer (S2) and wherein the hole is created by passing a needle through the reactive foam and optionally through the layer (S2), d) attaching at least one fiber (F) to the needle e) recycling the needle and fiber (F) through the hole so that the fiber (F) is in the body portion with the fiber portion (FB2) and
  • Reactive foam is enclosed, while the fiber region (FB1) of the fiber (F) protrudes from a first side of the shaped body or optionally from the layer (S2) and the fiber region (FB3) protrudes from a second side of the shaped body, f) optionally cutting off the fiber (F) on the second side and g) optionally cutting open the loop of the fiber (F) formed on the needle.
  • a hook needle is used as the needle and at least one fiber (F) hooked into the hook needle in step d).
  • a plurality of fibers (F) are simultaneously introduced into the reactive foam according to the previously described steps.
  • depressions in the shaped body are introduced partially or completely into the reactive foam before the introduction of at least one fiber (F).
  • the present invention further provides a process for the production of the panel according to the invention, in which the at least one layer (S1) is produced, applied and cured as reactive viscous resin on a molded body according to the invention, preferably by liquid impregnation, more preferably by pressure or vacuum assisted impregnation, especially preferably by vacuum infusion or pressure assisted injection methods, most preferably by vacuum infusion.
  • liquid impregnation methods are known to the person skilled in the art and are described, for example, in Wiley Encyclopedia of Composites (2nd Edition, Wiley, 2012), Parnas et al. (Liquid Composite Molding, Hanser, 2000) and Williams et al. (Composites Part A, 27, pp. 517-524, 1997).
  • auxiliary materials can be used to produce the panel according to the invention.
  • Suitable auxiliary materials for production by vacuum infusion are, for example, vacuum film, preferably nylon, vacuum sealing tape, flow aid, preferably nylon, release film, preferably polyolefin, tear-off fabric, preferably polyester and a semipermeable film, preferably a membrane film, more preferably a PTFE membrane film and Absaugvlies , preferably of polyester.
  • the choice of suitable auxiliary materials depends on the component to be manufactured, the selected process and the materials used, especially the resin system. When using resin systems based on epoxy and polyurethane, preference is given to using nylon flow aids, polyolefin release liners, polyester tear-off fabrics and semipermeable films as PTFE membrane sheets and polyester absorbent sheets.
  • auxiliary materials can be used in various ways in the processes for producing the panel according to the invention.
  • Panels are particularly preferably produced from the moldings by applying fiber-reinforced cover layers by means of vacuum infusion.
  • fibrous materials and optionally further layers are applied to the upper and lower sides of the molded bodies to produce the panel according to the invention.
  • tear-off fabric and release films are placed.
  • infusion of the liquid resin system can be used with flow aids and / or membrane films.
  • VAP structure semipermeable membrane
  • VAP structure semipermeable membrane
  • release film and Abr facedgewebe be used on one or both sides and the semipermeable membrane is sealed by vacuum sealing tape to the mold surface, the Absaugvlies is used on the molding foreign side of the semipermeable membrane whereby the air surface is evacuated to the top
  • a membrane bag vacuum bag which is preferably placed on the opposite sprue side of the molded body, evacuating the air from the opposite side to the gate.
  • the assembly is then fitted with sprues for the resin system and ports for evacuation. Finally, a vacuum film is applied over the entire structure, sealed with sealing tape and evacuated the entire structure. After infusion of the resin system, the reaction of the resin system takes place while maintaining the vacuum.
  • the present invention furthermore relates to the use of the shaped body or the panel according to the invention for rotor blades, in wind turbines, in the transport sector, in the construction sector, in the automotive industry, in shipbuilding, in rail vehicle construction, for container construction, for sanitary facilities and / or in the aerospace industry. and space travel.
  • Example 1 Comparative Example: Moldings of Reactively Produced PU Molded Foams Without Fiber Reinforcement The following components were used:
  • K1 -1 Mixture of diphenylmethane diisocyanate and polymethylene phenyl polyisocyanate with an isocyanate index of 130 and a
  • Viscosity of 200 mPa ⁇ s at 25 ° C. (according to DIN 53019)
  • K2-2 polypropylene oxide having a functionality of 2, a number average molecular weight M n of 1000 g / mol and a viscosity of 150 mPa ⁇ s
  • K2-3 pentaerythritol-based ethylene oxide having a functionality of 4, a number average molecular weight M n of 350 g / mol and a viscosity of 1000 mPa ⁇ s at 25 ° C .;
  • K2-4 phthalic anhydride / diethylene glycol-based with a functionality of 2, a number average molecular weight M n of 350 g / mol and a viscosity of 2500 mPa ⁇ s at 25 ° C. (according to DI N 53019)
  • Catalyst tertiary aliphatic amine
  • A-1 chain extender: propylene glycol based, weight average
  • A-2 Crosslinker: Glycerol-based, weight-average molecular weight M w of 94 g / mol
  • A-3 Stabilizer: Silicone-containing stabilizer for rigid polyurethane foam
  • the preparation of the reactive polyurethane foam according to the invention is carried out by the discontinuous foaming of the reactive mixtures in a mold.
  • the second component (K2) and the other additives, the catalyst and the other components are introduced, the first component (K1) is added and the mixture is mixed at room temperature with a suitable stirrer at 1800 U / min in an open vessel.
  • the parts by weight of the components are given in Table 1.
  • the resulting reactive mixture is then introduced into a suitably tempered mold at 45 ° C and cured to obtain a rigid polyurethane foam.
  • the polyurethane rigid foam obtained is cut into the required shape for further processing.
  • the basic geometry of the moldings obtained is given by the forming tool and described in more detail in the further description.
  • Table 1 Component parts by weight
  • the reactive foam and glass gels are used in addition to the resin systems used, the reactive foam and glass gels: nylon vacuum film, vacuum sealing tape, nylon flow aid, polyolefin release film, polyester tear off fabric and PTFE membrane film and polyester absorbent nonwoven.
  • Panels also referred to below as sandwich materials, are produced from the moldings by applying fiber-reinforced cover layers by means of vacuum infusion.
  • At the top and bottom of the (fiber-reinforced) foams are each two layers of Quadrax Glasgelege (Roving: E-Glass SE1500, OCV, textile: Saertex, isotropic laminate [0 -45 90 ° 45 °], each 1200 g / m 2 ) applied.
  • a release film is inserted between the molded body, hereinafter also referred to as core material, and the glass scrim, in contrast to the standard production of the panels.
  • core material a molded body
  • the glass scrim On the glass shelves the tear-off fabric and the flow aids are attached on both sides. The assembly is then fitted with sprues for the resin system and ports for evacuation. Finally, a Applied vacuum film over the entire structure, sealed with sealing tape and evacuated the entire structure.
  • the structure is prepared on an electrically heated table with a glass surface.
  • the resin system used is amine hardening epoxy (resin: BASF Baxxores 5400, hardener: BASF Baxxodur 5440, mixing ratio and further processing according to data sheet).
  • the resin is evacuated for 10 minutes at up to 20 mbar.
  • a resin temperature of 23 + / - 2 ° C infusion takes place on the pre-tempered structure (table temperature: 35 ° C).
  • subsequent temperature ramp of 0.3 K / min from 35 ° C to 75 ° C and isothermal curing at 75 ° C for 6 h panels can be made, which consist of the reactive foams and glass fiber reinforced cover layers.
  • the moldings are measured according to ISO 845 (as of October 2009) in order to obtain the density of the molded body.
  • the processed panels are trimmed to eliminate excess resin build-up in the marginal areas by improperly fitting vacuum foil.
  • the cover layers are removed and the moldings contained are measured again by ISO 845.
  • the difference of the densities results in the absolute resin absorption.
  • the corresponding resin absorption results in kg / m 2 .
  • V4 slotted plate by cutting ⁇ 5% 3.8 kg / m 2
  • Example 1 In order to improve the peel strength at the same time low resin absorption at the surface, the experiments of Example 1 are repeated, however, the molded body (reactive foam) is initially partially reinforced with glass fibers (rovings, S2-glass, 400 tex, AGY).
  • the glass fibers are introduced in the form of rovings at an angle ⁇ of 45 ° in four different spatial directions at an angle ⁇ to each other (0 °, 90 °, 180 °, 270 °). In all spatial directions, an identical number of glass fibers is introduced.
  • about 10 mm of the glass fibers are left on the cover layer on the supernatant on both sides in order to improve the connection to the glass fiber mats later introduced as cover layers.
  • the fiber or fiber rovings are introduced automatically by a combined sewing / crochet process.
  • a hook needle (diameter approx. 0.80 mm) is pierced completely from the first side to the second side of the particle foam.
  • a roving is hooked into the hook of the hook needle and then pulled from the second side through the needle back to the first side of the reactive foam.
  • the roving on the second side is cut off and the formed roving loop is cut on the needle.
  • the hook needle is thus ready for the next process.
  • the peel strength of the panels is determined with single cantilever beam (SCB) samples.
  • the thickness of the moldings is 20 mm, the layers (S1) each consist of about 2 mm thick, quasi-isotropic glass fiber reinforced epoxy resin. This results in a thickness of the panel of 24 mm.
  • the samples are tested in a Zwick Z050 tensile testing machine at a speed of 5 mm / min, whereby each test piece is loaded and unloaded several times (3 to 4 times).
  • the crack growth or the increase in each load cycle (Aa) is determined optically. From the Force-displacement curve determines the crack growth energy (AU). From this, the fracture toughness or peel strength is determined as
  • the peel strength in a panel can be increased significantly (B7 to B10) by means of the moldings with integrated fibers comprising a reactively produced PU molded foam according to the invention.
  • the fiber reinforcement of the reactive foam thus allows for a nearly identical resin absorption of the surface a significant increase in the peel strength.
  • the strength depends only slightly on the surface roughness or pretreatment and thus allows a decoupling of the two optimization goals peel strength and resin absorption.

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Abstract

The present invention relates to a moulded body made of a reactive foam material, at least one fiber (F) being located partly within the moulded body, i.e. being surrounded by the foam material. The two ends of the respective fiber (F) which are not surrounded by the reactive foam material thus protrude on one side of the corresponding moulded body. The reactive foam material is produced according to moulding foam method. The invention also relates to a panel which comprises at least one such moulded body and at least one additional layer (S1). The invention further relates to methods for the production of the moulded bodies from reactive foam material or to the panels according to the invention and to the use thereof, for example as rotor blades in wind turbines.

Description

Faserverstärkung von Reaktivschaumstoffen aus einem Formschäumverfahren Beschreibung Die vorliegende Erfindung betrifft einen Formkörper aus Reaktivschaumstoff, wobei sich mindestens eine Faser (F) teilweise innerhalb des Formkörpers befindet, also vom Reaktivschaumstoff umschlossen ist. Die beiden nicht vom Reaktivschaumstoff umschlossenen Enden der jeweiligen Faser (F) ragen somit aus jeweils einer Seite des entsprechenden Formkörpers heraus. Der Reaktivschaumstoff wird durch ein Formschäumverfahren hergestellt. Ein weiterer Gegenstand der vorliegenden Erfindung ist ein Paneel, das mindestens einen solchen Formkörper sowie mindestens eine weitere Schicht (S1 ) umfasst. Weitere Gegenstände der vorliegenden Erfindung sind Verfahren zur Herstellung der erfindungsgemäßen Formkörper aus Reaktivschaumstoff bzw. der erfindungsgemäßen Paneele sowie deren Verwendung, beispielsweise als Rotorblatt in Windenergieanlagen.  Description: The present invention relates to a shaped body made of reactive foam, wherein at least one fiber (F) is located partially within the shaped body, ie is enclosed by the reactive foam. The two ends of the respective fiber (F) not surrounded by the reactive foam thus protrude from one side of the corresponding shaped body. The reactive foam is produced by a foam molding process. Another object of the present invention is a panel comprising at least one such shaped body and at least one further layer (S1). Further objects of the present invention are methods for producing the shaped bodies according to the invention from reactive foam or the panels according to the invention and their use, for example as a rotor blade in wind turbines.
WO 2006/125561 betrifft ein Verfahren zur Herstellung von einem verstärkten zellulären Material, wobei in einem ersten Verfahrensschritt im zellulären Material mindestens ein Loch erzeugt wird, das sich von einer ersten Oberfläche zu einer zweiten Oberfläche des zellulären Materials erstreckt. Auf der anderen Seite, der zweiten Oberfläche des zellulären Materials, wird mindestens ein Faserbündel bereitgestellt, wobei dieses Faserbündel mit einer Nadel durch das Loch auf die erste Seite des zellulären Materials gezogen wird. Bevor die Nadel das Faserbündel fasst, wird die Nadel jedoch zunächst von der ersten Seite des zellulären Materials kommend durch das jeweilige Loch gezogen. Weiterhin befindet sich das Faserbündel mit Abschluss des Verfahrens gemäß WO 2006/125561 teilweise innerhalb des zellulären Materials, da es das entsprechende Loch ausfüllt, teilweise ragt das entsprechende Faserbündel auf den jeweiligen Seiten aus der ersten sowie zweiten Oberfläche des zellulären Materials heraus. WO 2006/125561 relates to a method for producing a reinforced cellular material, wherein in a first method step at least one hole is created in the cellular material extending from a first surface to a second surface of the cellular material. On the other side, the second surface of the cellular material, at least one fiber bundle is provided, this fiber bundle being pulled with a needle through the hole to the first side of the cellular material. However, before the needle grasps the fiber bundle, the needle is first pulled from the first side of the cellular material through the respective hole. Furthermore, with the completion of the method according to WO 2006/125561, the fiber bundle is partly located within the cellular material, since it fills the corresponding hole, in part the corresponding fiber bundle protrudes on the respective sides from the first and second surface of the cellular material.
Durch das in WO 2006/125561 beschriebene Verfahren können sandwichartige Komponenten hergestellt werden, die einen Kern aus besagtem zellulären Material sowie mindestens ein Faserbündel umfassen. An den Oberflächen dieses Kernes können Harzschichten und faserverstärkte Harzschichten aufgebracht werden, um die eigentliche sandwichartige Komponente herzustellen. Als zelluläres Material zur Ausbildung des Kerns der sandwichartigen Komponente können beispielsweise Polyvinylchloride oder Polyurethane eingesetzt werden. Als Faserbündel kommen beispielsweise Kohlenstofffasern, Nylonfasern, Glasfasern oder Polyesterfasern in Frage. The method described in WO 2006/125561 can be used to produce sandwich-type components comprising a core of said cellular material and at least one fiber bundle. On the surfaces of this core, resin layers and fiber-reinforced resin layers may be applied to produce the actual sandwich-type component. As the cellular material for forming the core of the sandwich-type component, polyvinyl chlorides or polyurethanes, for example, can be used. As a fiber bundle, for example, carbon fibers, nylon fibers, glass fibers or polyester fibers in question.
WO 2006/125561 offenbart jedoch nicht, dass Reaktivschaumstoffe, die durch ein Formschäumverfahren hergestellt werden, als zelluläres Material zur Herstellung eines Kerns in einer sandwichartigen Komponente verwendet werden können. Die sandwichartigen Komponenten gemäß WO 2006/125561 eignen sich zur Verwendung im Flugzeugbau. WO 201 1/012587 betrifft ein weiteres Verfahren zur Herstellung eines Kerns mit integrierten Brückenfasern für Paneele aus Kompositmaterialien. Der Kern wird hergestellt, indem durch einen so genannten„Kuchen" aus Leichtmaterial die auf einer Oberfläche des entsprechenden Kuchens bereitgestellten Brückenfasern mit Hilfe einer Nadel teilweise oder vollständig durchgezogen werden. Der „Kuchen" kann aus Polyurethanschäumen, Polyesterschäumen, Polyethylenterephthalatschäumen, Polyvinylchloridschäumen oder einem phenolischen Schaum, insbesondere aus einem Polyurethanschaum ausgebildet sein. Als Fasern können prinzipiell jegliche Art von einfachen oder mehrfachen Fäden sowie sonstige Garne verwendet werden. Die so hergestellten Kerne können wiederum Bestandteil eines Paneels aus Kompositmaterialien sein, wobei der Kern einseitig oder zweiseitig von einer Harzmatrix und Kombinationen aus Harzmatrizes mit Fasern in einer sandwichartigen Ausgestaltung umgeben ist. WO 201 1/012587 offenbart jedoch nicht, dass Reaktivschaumstoffe, die durch ein Formschäumverfahren hergestellt werden, zur Herstellung des entsprechenden Kernmaterials eingesetzt werden können. However, WO 2006/125561 does not disclose that reactive foams produced by a foam molding process are used as the cellular material for producing a foam Kerns can be used in a sandwich-like component. The sandwich-like components according to WO 2006/125561 are suitable for use in aircraft construction. WO 201 1/012587 relates to another process for producing a core with integrated bridge fibers for panels of composite materials. The core is made by partially or fully drawing through a bridle fiber provided on a surface of the respective cake by means of a needle through a so-called "cake" made of light material Foam, in particular be formed of a polyurethane foam. In principle, any type of single or multiple threads and other yarns can be used as the fibers. The cores thus produced may in turn be part of a panel of composite materials, wherein the core is surrounded on one or both sides by a resin matrix and combinations of resin matrices with fibers in a sandwich-like configuration. However, WO 201 1/012587 does not disclose that reactive foams produced by a foam molding process can be used to produce the corresponding core material.
WO 2012/138445 betrifft ein Verfahren zur Herstellung eines Komposit-Kernpaneels unter Verwendung einer Vielzahl von länglichen Streifen aus einem zellulären Material mit einer niedrigen Dichte. Zwischen die jeweiligen Streifen wird eine doppellagige Fasermatte eingebracht, die unter Verwendung von Harz ein Verkleben der einzelnen Streifen unter Ausbildung der Komposit-Kernpaneele bewirkt. Das zelluläre Material mit niedriger Dichte, das die länglichen Streifen ausbildet, ist gemäß WO 2012/138445 ausgewählt aus Balsaholz, elastischen Schäumen oder faserverstärkten Kompositschäumen. Bei den doppellagig zwischen den einzelnen Streifen eingebrachten Fasermatten kann es sich beispielsweise um eine poröse Glasfasermatte handeln. Das als Kleber verwendete Harz kann beispielsweise ein Polyester, ein Epoxy- oder ein phenolisches Harz sein oder ein durch Wärme aktivierter Thermoplast, beispielsweise Polypropylen oder PET. WO 2012/138445 offenbart jedoch nicht, dass als zelluläres Material für die verlängerten Streifen auch ein Reaktivschaumstoff, der durch ein Formschäumverfahren hergestellt wird, verwendet werden kann. Ebenso wenig ist darin offenbart, dass einzelne Fasern oder Faserbündel in das zelluläre Material zur Verstärkung eingebracht werden können. Gemäß WO 2012/138445 werden hierfür ausschließlich Fasermatten eingesetzt, die zudem ein Verbindungsglied im Rahmen einer Verklebung der einzelnen Streifen mittels Harz unter Erhalt des Kernmaterials darstellen. GB-A 2 455 044 offenbart ein Verfahren zur Herstellung eines mehrschichtigen Kompositartikels, wobei in einem ersten Verfahrensschritt eine Vielzahl von Pellets aus thermoplastischem Material sowie einem Treibmittel bereitgestellt werden. Das thermoplastische Material ist ein Gemisch aus Polystyrol (PS) und Polyphenylenoxid (PPO), das mindestens 20 bis 70 Gew.-% PPO enthält. In einem zweiten Verfahrensschritt werden die Pellets expandiert und in einem dritten Schritt in einer Form unter Ausbildung eines geschlossenzelligen Schaums aus dem thermoplastischen Material zu einem Formkörper verschweißt, wobei der geschlossenzellige Schaum die Gestalt der Form annimmt. Im nächsten Verfahrensschritt wird auf die Oberfläche des geschlossenzelligen Schaums eine Schicht aus faserverstärktem Material aufgebracht, wobei die Anbindung der jeweiligen Oberflächen unter Verwendung von einem Epoxidharz durchgeführt wird. GB-A 2 455 044 offenbart jedoch nicht, dass ein Fasermaterial in den Kern des mehrschichtigen Kompositartikels eingebracht werden kann. WO 2012/138445 relates to a method of making a composite core panel using a plurality of elongated strips of a low density cellular material. Between the respective strips a double-layered fiber mat is introduced which, by using resin, causes the individual strips to stick together to form the composite core panels. The cellular material of low density forming the elongated strips is selected according to WO 2012/138445 from balsa wood, elastic foams or fiber-reinforced composite foams. The double-layered fiber mats introduced between the individual strips may be, for example, a porous glass fiber mat. The resin used as the adhesive may be, for example, a polyester, an epoxy or a phenolic resin or a thermally activated thermoplastic, for example polypropylene or PET. However, WO 2012/138445 does not disclose that as a cellular material for the elongated strips, a reactive foam prepared by a foam molding process can also be used. Nor is it disclosed that single fibers or fiber bundles can be incorporated into the cellular material for reinforcement. According to WO 2012/138445 exclusively fiber mats are used for this purpose, which also represent a connecting member in the context of an adhesive bond of the individual strips by means of resin to obtain the core material. GB-A-2 455 044 discloses a method for producing a multilayer composite article, wherein in a first method step a plurality of pellets of thermoplastic material and a blowing agent are provided. The thermoplastic material is a mixture of polystyrene (PS) and polyphenylene oxide (PPO) containing at least 20 to 70 weight percent PPO. In a second process step, the pellets are expanded and welded in a third step in a mold to form a closed-cell foam of the thermoplastic material into a shaped body, wherein the closed-cell foam assumes the shape of the mold. In the next process step, a layer of fiber-reinforced material is applied to the surface of the closed-cell foam, the attachment of the respective surfaces being carried out using an epoxy resin. However, GB-A-2 455 044 does not disclose that a fibrous material can be incorporated into the core of the multilayer composite article.
Ein sinngemäßes Verfahren bzw. ein sinngemäßer mehrschichtiger Kompositartikel (wie in GB-A 2 455 044) ist auch in WO 2009/047483 offenbart. Diese mehrschichtigen Kompositartikel eignen sich beispielsweise zur Verwendung als Rotorblätter (in Windturbinen) oder als Bootrumpf. A similar method or an analogous multilayer composite article (as in GB-A 2 455 044) is also disclosed in WO 2009/047483. These multilayer composite articles are suitable, for example, for use as rotor blades (in wind turbines) or as boat hulls.
US-B 7,201 ,625 offenbart ein Verfahren zur Herstellung von Schaumprodukten sowie die Schaumprodukte als solche, die beispielsweise im Sportbereich als Surfbrett eingesetzt werden können. Den Kern des Schaumproduktes bildet ein Partikelschaum, beispielsweise auf Basis eines Polystyrolschaums. Dieser Partikelschaum wird in einer speziellen Form hergestellt, wobei eine Plastikaußenhaut den Partikelschaum umschließt. Die Plastikaußenhaut kann beispielsweise ein Polyethylenfilm sein. Auch US-B 7,201 ,625 offenbart jedoch nicht, dass im Partikelschaum Fasern zur Verstärkung des Materials enthalten sein können. US-B 6,767,623 offenbart Sandwichpaneele, die eine Kernschicht aus Polypropylenpartikelschaum auf der Basis von Partikeln mit einer Partikelgröße im Bereich von 2 bis 8 mm und einer Schüttdichte im Bereich von 10 bis 100 g/l aufweisen. Weiterhin umfassen die Sandwichpaneele zwei Deckschichten aus faserverstärktem Polypropylen, wobei die einzelnen Deckschichten so um den Kern angeordnet sind, dass ein Sandwich ausgebildet wird. Gegebenenfalls können noch weitere Schichten zu dekorativen Zwecken in den Sandwichpaneelen enthalten sein. Die Deckschichten können Glasfasern oder sonstige Polymerfasern enthalten. US Pat. No. 7,201,625 discloses a method for the production of foam products and the foam products as such, which can be used, for example, in sports as a surfboard. The core of the foam product forms a particle foam, for example based on a polystyrene foam. This particle foam is produced in a special form, wherein a plastic outer skin encloses the particle foam. The plastic outer skin can be, for example, a polyethylene film. However, US Pat. No. 7,201,625 does not disclose that fibers for reinforcing the material can be contained in the particle foam. US-B 6,767,623 discloses sandwich panels comprising a core layer of polypropylene particle foam based on particles having a particle size in the range of 2 to 8 mm and a bulk density in the range of 10 to 100 g / l. Furthermore, the sandwich panels comprise two cover layers of fiber-reinforced polypropylene, wherein the individual cover layers are arranged around the core, that a sandwich is formed. Optionally, further layers may be included for decorative purposes in the sandwich panels. The cover layers may contain glass fibers or other polymer fibers.
EP-A 2 420 531 offenbart Extrusionsschaumstoffe auf Basis eines Polymers wie Polystyrol, in denen mindestens ein mineralischer Füllstoff mit einer Partikelgröße von < 10 μηη und mindestens ein Keimbildner enthalten sind. Diese Extrusionsschaumstoffe zeichnen sich durch ihre verbesserte Steifigkeit aus. Weiterhin wird ein entsprechendes Extrusionsverfahren zur Herstellung solcher Extrusionsschaumstoffe auf Basis von Polystyrol beschrieben. Die Extrusionsschaumstoffe können geschlossenzellig sein. Die EP-A 2 480 531 beschreibt allerdings nicht, dass die Extrusionsschaumstoffe Fasern enthalten. EP-A 2 420 531 discloses extruded foams based on a polymer such as polystyrene, in which at least one mineral filler with a particle size of <10 μm and at least one nucleating agent are present. These extrusion foams are characterized by their improved rigidity. Furthermore, a corresponding extrusion process for producing such extruded foams based on polystyrene is described. The extrusion foams may be closed cell. However, EP-A 2 480 531 does not describe that the extrusion foams contain fibers.
WO 2005/056653 betrifft Partikelschaumstoffformteile aus expandierbaren, Füllstoff enthaltenden Polymergranulaten. Die Partikelschaumstoffformteile sind erhältlich durch Verschweißen von vorgeschäumten Schaumpartikeln aus expandierbaren, Füllstoff enthaltenden, thermoplastischen Polymergranulaten, wobei der Partikelschaumstoff eine Dichte im Bereich von 8 bis 300 g/l aufweist. Bei den thermoplastischen Polymergranulaten handelt es sich insbesondere um ein Styrolpolymer. Als Füllstoff können pulverförmige anorganische Stoffe, Metall, Kreide, Aluminiumhydroxid, Kalziumcarbonat oder Tonerde oder kugel- oder faserförmige anorganische Stoffe wie Glaskugeln, Glasfasern oder Kohlefasern eingesetzt werden. WO 2005/056653 relates to particle foam moldings made of expandable polymer granules containing filler. The particle foam moldings are obtainable by welding prefoamed foam particles of expandable, filler-containing, thermoplastic polymer granules, wherein the particle foam has a density in the range of 8 to 300 g / l. The thermoplastic polymer granules are in particular a styrene polymer. As filler, powdery inorganic substances, metal, chalk, aluminum hydroxide, calcium carbonate or alumina or spherical or fibrous inorganic substances such as glass beads, glass fibers or carbon fibers can be used.
Die US 3,030,256 beschreibt laminierte Paneele sowie ein Verfahren zu deren Herstellung. Die Paneele umfassen ein Kernmaterial, in das Faserbündel eingebracht werden, sowie Oberflächenmaterialien. Die Kernmaterialien sind geschäumter Plastik und expandierter Plastik. Die Fasern befinden sich mit einem Faserbereich innerhalb des Schaumstoffs. Ein erster Faserbereich ragt aus der ersten Seite des Formkörpers heraus, ein zweiter Faserbereich aus der zweiten Seite des Formkörpers. US 3,030,256 describes laminated panels and a method for their production. The panels include a core material into which fiber bundles are introduced and surface materials. The core materials are foamed plastic and expanded plastic. The fibers are located within a fiber region within the foam. A first fiber region protrudes from the first side of the molding, a second fiber region protrudes from the second side of the molding.
Die US 6, 187,41 1 betrifft verstärkte Sandwich-Paneele, die ein Schaumstoffkernmaterial, das auf beiden Seiten eine Faserschicht aufweist, und Fasern, die durch die äußeren Faserschichten und den Schaumstoff hindurch gestochen werden, umfasst. Als Schaumstoffkernmaterialien sind Polyurethane, Phenole und Isocyanate beschrieben. Die US 2010/0196652 betrifft quasi isotrope Sandwich-Strukturen, die ein Kernmaterial umfassen, das von Fasermatten umgeben ist, wobei Glasfaserrovings in die Fasermatten und das Kernmaterial gestochen sind. Als Schaumstoffe sind verschiedene Schaumstoffe, wie beispielsweise Polyurethan, Polyisocyanurat, Phenole, Polystyrol, PEI , Polyethylen, Polypropylen und ähnliche beschrieben. US 6,187,411 relates to reinforced sandwich panels comprising a foam core material having a fibrous layer on both sides and fibers which are pierced through the outer fibrous layers and the foam. Foamed core materials are polyurethanes, phenols and isocyanates. US 2010/0196652 relates to quasi-isotropic sandwich structures comprising a core material surrounded by fiber mats with glass fiber rovings pricking into the fiber mats and the core material. As foams, various foams, such as polyurethane, polyisocyanurate, phenols, polystyrene, PEI, polyethylene, polypropylene and the like are described.
Nachteilig bei den in US 3,030,256, US 6,187,41 1 und US 2010/0196652 beschriebenen Kompositmaterialien ist, dass diese häufig eine hohe Harzaufnahme aufweisen. Für die Herstellung von Reaktivschäumen gibt es eine Vielzahl unterschiedlicher Herstellverfahren, Materialien und daraus resultierende Eigenschaften. Eine Übersicht ist beispielsweise in 'Polyurethane and related foams', K. Ashida, 2006, CRC, in Polyurethane Handbook, G. Oertel, 1994, 2nd edition, Hanser und in Szycher's Handbook of Polyurethanes, M. Szycher, 2012, 2nd edition, CRC, gegeben. Die der vorliegenden Erfindung zugrunde liegende Aufgabe besteht in der Bereitstellung von neuen faserverstärkten Formkörpern bzw. Paneelen. A disadvantage of the composite materials described in US Pat. No. 3,030,256, US Pat. No. 6,187,411 and US 2010/0196652 is that they frequently have a high resin uptake. For the production of reactive foams, there are a variety of different manufacturing processes, materials and resulting properties. An overview for example, in 'Polyurethanes and related foams', K. Ashida, 2006, CRC, in Polyurethane Handbook, G. Oertel, 1994, 2nd edition, Hanser and in Szycher's Handbook of Polyurethanes, M. Szycher, 2012, 2nd edition, CRC, given. The object underlying the present invention is to provide new fiber-reinforced moldings or panels.
Gelöst wird diese Aufgabe erfindungsgemäß durch einen Formkörper aus Reaktivschaumstoff, bei dem mindestens eine Faser (F) sich mit einem Faserbereich (FB2) innerhalb des Formkörpers befindet und von dem Reaktivschaumstoff umschlossen ist, während ein Faserbereich (FB1 ) der Faser (F) aus einer ersten Seite des Formkörpers herausragt und ein Faserbereich (FB3) der Faser (F) aus einer zweiten Seite des Formkörpers herausragt, wobei der Reaktivschaumstoff nach einem Formschäumverfahren hergestellt ist, wobei die Faser (F) in einem Winkel α von 10 bis 70° relativ zur Dickenrichtung (d) des Formkörpers in den Reaktivschaumstoff eingebracht ist und wobei der Formkörper erhältlich ist nach einem Verfahren umfassend die Schritte a) bis f): a) gegebenenfalls Aufbringen von mindestens einer Schicht (S2) auf mindestens eine Seite des Reaktivschaumstoffs, b) Erzeugung von einem Loch je Faser (F) im Reaktivschaumstoff und gegebenenfalls der Schicht (S2), wobei sich das Loch von einer ersten Seite zu einer zweiten Seite des Reaktivschaumstoffs und gegebenenfalls durch die Schicht (S2) erstreckt, c) Bereitstellung von mindestens einer Faser (F) auf der zweiten Seite des Reaktivschaumstoffs, d) Durchführen einer Nadel von der ersten Seite des Reaktivschaumstoffs durch das Loch zur zweiten Seite des Reaktivschaumstoffs und gegebenenfalls Durchführen der Nadel durch die Schicht (S2), e) Befestigen von mindestens einer Faser (F) an der Nadel auf der zweiten Seite des Reaktivschaumstoffs, und f) Rückführen der Nadel samt Faser (F) durch das Loch, so dass die Faser (F) sich mit dem Faserbereich (FB2) innerhalb des Formkörpers befindet und von dem Reaktivschaumstoff umschlossen ist, während der Faserbereich (FB1 ) der Faser (F) aus einer ersten Seite des Formkörpers oder gegebenenfalls aus der Schicht (S2) herausragt und der Faserbereich (FB3) der Faser (F) aus einer zweiten Seite des Formkörpers herausragt. This object is achieved according to the invention by a molded body of reactive foam, wherein at least one fiber (F) is located with a fiber region (FB2) within the molding and is enclosed by the reactive foam, while a fiber region (FB1) of the fiber (F) from a protruding first side of the molded body and a fiber portion (FB3) of the fiber (F) protrudes from a second side of the shaped body, wherein the reactive foam is produced by a foam molding process, wherein the fiber (F) at an angle α of 10 to 70 ° relative to Thickness direction (d) of the shaped body is introduced into the reactive foam and wherein the shaped body is obtainable by a process comprising the steps a) to f): a) optionally applying at least one layer (S2) on at least one side of the reactive foam, b) production from a hole per fiber (F) in the reactive foam and optionally the layer (S2), wherein the hole of a c) providing at least one fiber (F) on the second side of the reactive foam, d) passing a needle from the first side of the reactive foam through the hole to the first side of the reactive foam e) attaching at least one fiber (F) to the needle on the second side of the reactive foam, and f) returning the needle and fiber (F) through the hole in that the fiber (F) is located with the fiber region (FB2) inside the molding and is enclosed by the reactive foam, while the fiber region (FB1) of the fiber (F) consists of a first side of the molding or optionally of the layer (S2 ) and stands out the fiber region (FB3) of the fiber (F) protrudes from a second side of the molding.
Gegenstand der vorliegenden Erfindung ist außerdem ein Formkörper aus Reaktivschaumstoff, bei dem mindestens eine Faser (F) sich mit einem Faserbereich (FB2) innerhalb des Formkörpers befindet und von dem Reaktivschaumstoff umschlossen ist, während ein Faserbereich (FB1 ) der Faser (F) aus einer ersten Seite des Formkörpers herausragt und ein Faserbereich (FB3) der Faser (F) aus einer zweiten Seite des Formkörpers herausragt, wobei der Reaktivschaumstoff nach einem Formschäumverfahren hergestellt ist. The subject of the present invention is also a shaped body of reactive foam in which at least one fiber (F) is located within the shaped body with a fiber region (FB2) and is enclosed by the reactive foam, while a fiber region (FB1) of the fiber (F) consists of a protrudes first side of the shaped body and a fiber region (FB3) of the fiber (F) protrudes from a second side of the shaped body, wherein the reactive foam is prepared by a foam molding process.
Anders ausgedrückt ist der Reaktivschaumstoff nach einem Formschäumverfahren erhältlich. Die erfindungsgemäßen Formkörper zeichnen sich in vorteilhafter Weise durch eine geringe Harzaufnahme bei gleichzeitig guter Grenzflächenanbindung aus, wobei die geringe Harzaufnahme insbesondere auf den Reaktivschaumstoff, hergestellt nach einem Formschäumverfahren, zurückzuführen ist. Dieser Effekt ist insbesondere dann von Bedeutung, wenn die erfindungsgemäßen Formkörper zu den erfindungsgemäßen Paneelen weiterverarbeitet werden. In other words, the reactive foam is obtainable by a foam molding process. The moldings according to the invention are advantageously characterized by a low resin absorption and at the same time good interfacial bonding, wherein the low resin absorption is due in particular to the reactive foam produced by a foam molding process. This effect is of particular importance when the shaped bodies according to the invention are further processed into the panels according to the invention.
Eine weitere Verbesserung der Anbindung bei gleichzeitig reduzierter Harzaufnahme wird erfindungsgemäß durch die Faserverstärkung der Reaktivschaumstoffe in den erfindungsgemäßen Formkörpern bzw. den daraus resultierenden Paneelen ermöglicht. Erfindungsgemäß können die Fasern (einzeln oder vorzugsweise als Faserbündel) in vorteilhafter Weise zunächst trocken und/oder durch mechanische Prozesse in den Reaktivschaumstoff eingebracht werden. Die Fasern bzw. Faserbündel werden an den jeweiligen Reaktivschaumstoffoberflächen nicht bündig, sondern mit Überstand abgelegt und ermöglichen damit eine verbesserte Anbindung bzw. eine direkte Verbindung mit den entsprechenden Decklagen im erfindungsgemäßen Paneel. Dies ist insbesondere dann der Fall, wenn als Decklage erfindungsgemäß mindestens eine weitere Schicht (S1 ) unter Ausbildung eines Paneels auf die erfindungsgemäßen Formkörper aufgebracht wird. Vorzugsweise werden zwei Schichten (S1 ), die gleich oder verschieden sein können, aufgebracht. Besonders bevorzugt werden zwei gleiche Schichten (S1 ), insbesondere zwei gleiche faserverstärkte Harzschichten, auf einander gegenüberliegenden Seiten des erfindungsgemäßen Formkörpers unter Ausbildung eines erfindungsgemäßen Paneels aufgebracht. Solche Paneele werden auch als „Sandwichmaterialien" bezeichnet, wobei der erfindungsgemäße Formkörper auch als„Kernmaterial" bezeichnet werden kann. Die erfindungsgemäßen Paneele zeichnen sich somit durch eine geringe Harzaufnahme in Verbindung mit einer guten Schälfestigkeit sowie einer guten Schubsteifigkeit und einem hohen Schubmodul aus. Weiterhin sind hohe Festigkeitsund Steifigkeitseigenschaften gezielt durch die Wahl der Fasertypen, deren Anteil und Anordnung einstellbar. Der Effekt einer geringen Harzaufnahme ist deswegen von Bedeutung, weil beim Einsatz von solchen Paneelen (Sandwichmaterialien) häufig das Ziel besteht, dass die strukturellen Eigenschaften bei möglichst geringem Gewicht erhöht werden sollen. Beim Einsatz von beispielsweise faserverstärkten Decklagen trägt neben den eigentlichen Decklagen und dem Formkörper (Sandwichkern) die Harzaufnahme des Formkörpers (Kernmaterials) zum Gesamtgewicht bei. Durch die erfindungsgemäßen Formkörper bzw. die erfindungsgemäßen Paneele kann die Harzaufnahme jedoch verringert werden, wodurch Gewicht sowie Kosten eingespart werden können. Als besonderer Vorteil kann in einer Ausführungsform der erfindungsgemäßen Formkörper die geschlossene Oberfläche des Reaktivschaumstoffs angesehen werden. Nach der Herstellung des Reaktivschaumstoffs durch ein Formschäumverfahren liegt in der Regel eine versiegelte (geschlossene) Oberfläche mit hoher Oberflächengüte vor, die sich durch minimale Harzaufnahme und einen Dichtegradienten, ausgehend vom Kern des Reaktivschaumstoffs hin zur Oberfläche, auszeichnet, wobei die Dichte vom Kern des Reaktivschaumstoffs zu dessen Oberfläche zunimmt. Ein Reaktivschaumstoff mit einem Dichtegradienten, wobei die Dichte vom Kern des Reaktivschaumstoffs zu dessen Oberfläche hin zunimmt, wird auch als Integralschaumstoff bezeichnet. Insbesondere durch Kombination mit den eingebrachten Fasern zum Erhalt der erfindungsgemäßen Formkörper kann somit minimales Gewicht bei maximalen mechanischen Eigenschaften erzielt werden. A further improvement of the connection with simultaneously reduced resin absorption is made possible by the fiber reinforcement of the reactive foams in the moldings according to the invention or the resulting panels. According to the invention, the fibers (individually or preferably as fiber bundles) can advantageously be introduced first of all dry and / or by mechanical processes into the reactive foam. The fibers or fiber bundles are not flush to the respective reactive foam surfaces, but deposited with supernatant and thus allow an improved connection or a direct connection with the corresponding cover layers in the panel according to the invention. This is the case in particular if, as cover layer, according to the invention at least one further layer (S1) is applied to the shaped bodies according to the invention with the formation of a panel. Preferably, two layers (S1), which may be the same or different, are applied. Particularly preferably, two identical layers (S1), in particular two identical fiber-reinforced resin layers, are applied to opposite sides of the molded body according to the invention to form a panel according to the invention. Such panels are also referred to as "sandwich materials", wherein the shaped body according to the invention can also be referred to as "core material". The panels of the invention are thus characterized by a low resin absorption in conjunction with a good peel strength and a good shear stiffness and a high shear modulus. Furthermore, high strength and stiffness properties are specifically adjusted by the choice of fiber types, their proportion and arrangement. The effect of a low resin absorption is important because when using such panels (sandwich materials) often the goal is that the structural properties should be increased with the lowest possible weight. When using, for example, fiber-reinforced cover layers, in addition to the actual cover layers and the molded body (sandwich core), the resin absorption of the shaped body (core material) contributes to the overall weight. However, due to the shaped bodies according to the invention or the panels according to the invention, the resin absorption can be reduced, as a result of which weight and costs can be saved. As a particular advantage, in one embodiment of the shaped body according to the invention, the closed surface of the reactive foam can be considered. After the reactive foam is produced by a foam molding process, there is typically a sealed (closed) surface of high surface quality, characterized by minimal resin uptake and a density gradient from the core of the reactive foam towards the surface, the density being from the core of the reactive foam increases to its surface. A reactive foam having a density gradient wherein the density increases from the core of the reactive foam towards its surface is also referred to as integral foam. In particular, by combining with the introduced fibers to obtain the moldings of the invention thus minimal weight can be achieved with maximum mechanical properties.
Unter dem Begriff „geschlossene Oberfläche" wird im Rahmen der vorliegenden Erfindung folgendes verstanden: Die geschlossene Oberfläche wird durch Licht- oder elektronenmikroskopische Aufnahmen ausgewertet. Anhand von Bildanalysen wird der Flächenanteil der geöffneten Schaumzellen, bezogen auf die Gesamtoberfläche, bewertet. Reaktivschäume mit geschlossener Oberfläche sind definiert als: (1 - Flächenanteil der geöffneten Schaumzellen)/Gesamtoberfläche > 30 %, vorzugsweise > 50 %, mehr bevorzugt > 80 %, insbesondere > 95 %. In the context of the present invention, the term "closed surface" is understood to mean the following: The closed surface is evaluated by light or electron microscopic images defined as: (1 - area fraction of the opened foam cells) / total surface area> 30%, preferably> 50%, more preferably> 80%, in particular> 95%.
Ein weiterer Vorteil der erfindungsgemäßen Formkörper bzw. Paneele ist darin zu sehen, dass aufgrund der Verwendung von Reaktivschaumstoffen bzw. der damit verbundenen Herstellung das Anbringen von integrierten Strukturen wie Schlitzen oder Löchern auf den Oberflächen der Formkörper sowie die Weiterverarbeitung der Formkörper relativ einfach ist. Durch die Fertigung lassen sich Strukturen direkt im Prozess durch formgebende Schritte wie Thermoformen oder spanende Bearbeitung integrieren. Derartige Strukturen werden beim Einsatz von solchen Formkörpern (Kernmaterialien) beispielsweise häufig zum Drapieren in gekrümmte Strukturen (tiefe Schlitze), zur Verbesserung der Verarbeitbarkeit durch Flüssigharzprozesse wie der Vakuuminfusion (Löcher) und zur Beschleunigung der genannten Verarbeitungsprozess (flache Schlitze) eingebracht. Die eingebrachten Strukturen weisen vorzugsweise ebenfalls eine geschlossene Oberfläche und damit eine sehr geringe oder sogar gar keine Harzaufnahme auf. A further advantage of the shaped bodies or panels according to the invention is that due to the use of reactive foams or the production associated therewith, the attachment of integrated structures such as slots or holes on the surfaces of the shaped bodies as well as the further processing of the shaped bodies is relatively simple. By manufacturing structures directly in the process by shaping steps such as thermoforming or machining integrate. For example, such structures are often used in draping curved structures (deep slits), improving workability by liquid resin processes such as vacuum infusion (holes), and accelerating the aforementioned processing (shallow slits) when using such moldings (core materials). The introduced structures also preferably have a closed surface and thus a very low or even no resin absorption.
Weiterhin können bei oder nach der Fertigung weitere Schichten (S2) auf den Reaktivschaumstoff aufgebracht werden. Derartige Schichten (S2) verbessern den Gesamtzusammenhalt des Reaktivschaumstoffs bzw. des erfindungsgemäßen Formkörpers. Furthermore, further layers (S2) can be applied to the reactive foam during or after production. Such layers (S2) improve the overall cohesion of the reactive foam or the molding according to the invention.
Weitere Verbesserungen/Vorteile können dadurch erzielt werden, dass die Fasern (F) in einem Winkel α im Bereich von 10° bis 70° in Bezug zur Dickenrichtung (d) des Reaktivschaumstoffs in den Reaktivschaumstoff eingebracht werden, besonders bevorzugt von 30° bis 50°. Generell ist das Einbringen der Fasern (F) in einem Winkel α von 0°bis < 90° technisch automatisiert durchführbar. Zusätzliche Verbesserungen/Vorteile können erzielt werden, wenn die Fasern (F) nicht nur parallel zueinander in den Reaktivschaumstoff eingebracht werden, sondern weitere Fasern (F) in einem Winkel ß zueinander, der vorzugsweise im Bereich von > 0 bis 180° liegt. Dadurch wird zusätzlich eine gezielte Verbesserung der mechanischen Eigenschaften des erfindungsgemäßen Formkörpers in unterschiedlichen Richtungen erreicht. Further improvements / advantages can be achieved by introducing the fibers (F) into the reactive foam at an angle α in the range from 10 ° to 70 ° with respect to the thickness direction (d) of the reactive foam, more preferably from 30 ° to 50 ° , In general, the introduction of the fibers (F) at an angle α of 0 ° to <90 ° is technically automated feasible. Additional improvements / advantages can be achieved if the fibers (F) are introduced into the reactive foam not only parallel to each other, but other fibers (F) at an angle β to each other, which is preferably in the range of> 0 to 180 °. As a result, a targeted improvement of the mechanical properties of the molding according to the invention in different directions is additionally achieved.
Ebenso ist es von Vorteil, wenn in den erfindungsgemäßen Paneelen die Harz(deck)schicht durch Flüssiginjektionsverfahren oder Flüssiginfusionsverfahren aufgebracht wird, bei dem die Fasern während der Verarbeitung mit Harz getränkt und die mechanischen Eigenschaften verbessert werden können. Zudem können dadurch Kosten eingespart werden. It is also advantageous if in the panels of the invention, the resin (cover) layer is applied by liquid injection or liquid infusion process, in which the fibers can be impregnated with resin during processing and the mechanical properties can be improved. In addition, this can be cost savings.
Nachfolgend wird die vorliegende Erfindung weiter präzisiert. Erfindungsgemäß umfasst der Formkörper einen Reaktivschaumstoff und mindestens eine Faser (F). Hereinafter, the present invention will be further clarified. According to the invention, the shaped body comprises a reactive foam and at least one fiber (F).
Die im Formkörper enthaltene Faser (F) ist eine einzelne Faser oder ein Faserbündel, vorzugsweise ein Faserbündel. Als Faser (F) eignen sich alle dem Fachmann bekannten Materialien, die Fasern bilden können. Beispielsweise ist die Faser (F) eine organische, anorganische, metallische, keramische Faser oder eine Kombination daraus, bevorzugt eine polymere Faser, Basaltfaser, Glasfaser, Kohlenstofffaser oder Naturfaser, insbesondere bevorzugt eine Polyaramidfaser, Glasfaser, Basaltfaser oder Kohlenstofffaser, eine polymere Faser ist vorzugsweise eine Faser aus Polyester, Polyamid, Polyaramid, Polyethylen, Polyurethan, Polyvinylchlorid, Polyimid und/oder Polyamidimid, eine Naturfaser ist vorzugsweise eine Faser aus Sisal, Hanf, Flachs, Bambus, Kokos und/oder Jute. The fiber (F) contained in the shaped body is a single fiber or a fiber bundle, preferably a fiber bundle. As fiber (F) are all known in the art materials that can form fibers. For example, the fiber (F) is an organic, inorganic, metallic, ceramic fiber or a combination preferably a polymeric fiber, basalt fiber, glass fiber, carbon fiber or natural fiber, more preferably a polyaramid fiber, glass fiber, basalt fiber or carbon fiber, a polymeric fiber is preferably a fiber of polyester, polyamide, polyaramid, polyethylene, polyurethane, polyvinyl chloride, polyimide and / or Polyamide-imide, a natural fiber is preferably a fiber of sisal, hemp, flax, bamboo, coconut and / or jute.
In einer Ausführungsform werden Faserbündel eingesetzt. Die Faserbündel setzen sich aus mehreren einzelnen Fasern (Filamenten) zusammen. Die Anzahl der Einzelfasern pro Bündel beträgt mindestens 10, bevorzugt 100 bis 100 000, besonders bevorzugt 300 bis 10 000 bei Glasfasern und 1000 bis 50 000 bei Kohlenstofffasern, und insbesondere bevorzugt 500 bis 5 000 bei Glasfasern und 2000 bis 20 000 bei Kohlenstofffasern. Erfindungsgemäß befindet sich die mindestens eine Faser (F) mit einem Faserbereich (FB2) innerhalb des Formkörpers und ist von dem Reaktivschaumstoff umschlossen, während ein Faserbereich (FB1 ) der Faser (F) aus einer ersten Seite des Formkörpers herausragt und ein Faserbereich (FB3) der Faser (F) aus einer zweiten Seite des Formkörpers herausragt. In one embodiment, fiber bundles are used. The fiber bundles are composed of several individual fibers (filaments). The number of single fibers per bundle is at least 10, preferably 100 to 100,000, more preferably 300 to 10,000 in glass fibers and 1,000 to 50,000 in carbon fibers, and more preferably 500 to 5,000 in glass fibers and 2,000 to 20,000 in carbon fibers. According to the invention, the at least one fiber (F) with a fiber region (FB2) is located inside the molding and is enclosed by the reactive foam, while a fiber region (FB1) of the fiber (F) protrudes from a first side of the molding and a fiber region (FB3) the fiber (F) protrudes from a second side of the shaped body.
Der Faserbereich (FB1 ), der Faserbereich (FB2) und der Faserbereich (FB3) können jeweils einen beliebigen Anteil der Gesamtlänge der Faser (F) ausmachen. In einer Ausführungsform machen der Faserbereich (FB1 ) und der Faserbereich (FB3) jeweils unabhängig voneinander 1 bis 45 %, vorzugsweise 2 bis 40 % und besonders bevorzugt 5 bis 30 %, und der Faserbereich (FB2) 10 bis 98 %, vorzugsweise 20 bis 96 %, besonders bevorzugt 40 bis 90 % der Gesamtlänge der Faser (F) aus. The fiber region (FB1), the fiber region (FB2) and the fiber region (FB3) can each make up an arbitrary fraction of the total length of the fiber (F). In one embodiment, the fiber region (FB1) and the fiber region (FB3) each independently form 1 to 45%, preferably 2 to 40% and more preferably 5 to 30%, and the fiber region (FB2) 10 to 98%, preferably 20 to 96%, more preferably 40 to 90% of the total length of the fiber (F).
In einer weiteren bevorzugten Ausführungsform liegt die erste Seite des Formkörpers, aus der der Faserbereich (FB1 ) der Faser (F) herausragt, der zweiten Seite des Formkörpers gegenüber, aus der der Faserbereich (FB3) der Faser (F) herausragt. In a further preferred embodiment, the first side of the shaped body, from which the fiber region (FB1) of the fiber (F) protrudes, faces the second side of the shaped body, from which the fiber region (FB3) of the fiber (F) protrudes.
Die Faser (F) ist in einem Winkel α von 10 bis 70° relativ zu Dickenrichtung (d) des Formkörpers bzw. zur Orthogonalen (der Oberfläche) der ersten Seite (2) des Formkörpers in den Formkörper eingebracht. The fiber (F) is introduced at an angle α of 10 to 70 ° relative to the thickness direction (d) of the molding or to the orthogonal (the surface) of the first side (2) of the molding in the molding.
Bevorzugt ist die Faser (F) in einem Winkel α von 30 bis 60°, vorzugsweise von 30 bis 50°, noch mehr bevorzugt von 30 bis 45°, insbesondere von 45° relativ zur Dickenrichtung (d) des Formkörpers in den Reaktivschaumstoff eingebracht. In einer weiteren Ausführungsform kann Winkel α beliebige Werte von 0 bis 90° annehmen. Beispielsweise ist die Faser (F) dann in einem Winkel α von 0 bis 60°, vorzugsweise von 0 bis 50°, mehr bevorzugt von 0 bis 15° oder von 10 bis 70 °, bevorzugt von 30 bis 60 °, besonders bevorzugt von 30 bis 50°, noch mehr bevorzugt von 30 bis 45°, insbesondere von 45°, relativ zur Dickenrichtung (d) des Formkörpers in den Reaktivschaumstoff eingebracht. The fiber (F) is preferably introduced into the reactive foam at an angle α of 30 to 60 °, preferably 30 to 50 °, more preferably 30 to 45 °, in particular 45 °, relative to the thickness direction (d) of the shaped body. In a further embodiment, angle α can assume any values from 0 to 90 °. For example, the fiber (F) is then at an angle α of 0 to 60 °, preferably from 0 to 50 °, more preferably from 0 to 15 ° or from 10 to 70 °, preferably from 30 to 60 °, more preferably from 30 to 50 °, even more preferably from 30 to 45 °, in particular from 45 °, introduced relative to the thickness direction (d) of the molding in the reactive foam.
In einer weiteren Ausführungsform werden zumindest zwei Fasern (F) in zwei unterschiedlichen Winkeln α, a-i und a2, eingebracht, wobei der erste Winkel α-ι vorzugsweise im Bereich von 0° bis 15° und der zweite Winkel a2 vorzugsweise im Bereich von 30 bis 50° liegt, insbesondere bevorzugt liegt a-i im Bereich von 0° bis 5° und a2 im Bereich von 40 bis 50°. In a further embodiment, at least two fibers (F) in two different angles α, ai and a 2 , introduced, wherein the first angle α-ι preferably in the range of 0 ° to 15 ° and the second angle a 2 preferably in the range of Is 30 to 50 °, more preferably ai is in the range of 0 ° to 5 ° and a 2 in the range of 40 to 50 °.
Bevorzugt werden alle Fasern (F) in einem Winkel α im Bereich von 10 bis 70°, bevorzugt von 30 bis 60°, insbesondere bevorzugt im Bereich von 30 bis 50°, noch mehr bevorzugt von 30 bis 45°, am meisten bevorzugt von 45° relativ zur Dickenrichtung (d) des Formkörpers in den Reaktivschaumstoff eingebracht. All fibers (F) are preferred at an angle α in the range of 10 to 70 °, preferably 30 to 60 °, more preferably in the range of 30 to 50 °, even more preferably 30 to 45 °, most preferably 45 ° relative to the thickness direction (d) of the molding introduced into the reactive foam.
Es ist darüber hinaus bevorzugt, dass außer der mindestens einen Faser (F) keine weitere Faser (F) in den Reaktivschaumstoff eingebracht ist. Vorzugsweise enthält ein erfindungsgemäßer Formkörper eine Vielzahl von Fasern (F), vorzugsweise als Faserbündel, und/oder umfasst mehr als 10 Fasern (F) oder Faserbündel pro m2, bevorzugt mehr als 1000 pro m2, besonders bevorzugt 4000 bis 40 000 pro m2. Vorzugsweise weisen sämtliche Fasern (F) im erfindungsgemäßen Formkörper den gleichen Winkel α oder zumindest einen annähernd gleichen Winkel (Abweichung von maximal +/- 5°, vorzugsweise +/- 2°, besonders bevorzugt +/- 1 °) auf. It is furthermore preferred that, apart from the at least one fiber (F), no further fiber (F) is introduced into the reactive foam. Preferably, a shaped body according to the invention contains a multiplicity of fibers (F), preferably as fiber bundles, and / or comprises more than 10 fibers (F) or fiber bundles per m 2 , preferably more than 1000 per m 2 , particularly preferably 4000 to 40 000 per m 2 . Preferably, all the fibers (F) in the molding according to the invention have the same angle α or at least approximately the same angle (deviation of at most + / - 5 °, preferably + / - 2 °, more preferably + / - 1 °).
Sämtliche Fasern (F) können parallel zueinander im Formkörper vorliegen. Ebenso ist es möglich und erfindungsgemäß bevorzugt, dass zwei oder mehr Fasern (F) in einem Winkel ß zueinander in dem Formkörper vorliegen. Unter dem Winkel ß wird im Rahmen der vorliegenden Erfindung der Winkel zwischen der senkrechten Projektion einer ersten Faser (F1 ) auf die Oberfläche der ersten Seite des Formkörpers und der senkrechten Projektion einer zweiten Faser (F2) auf die Oberfläche des Formkörpers verstanden, wobei beide Fasern in den Formkörper eingebracht sind. Der Winkel ß liegt vorzugsweise im Bereich ß = 360 n, wobei n eine ganzzahlige Zahl ist. Bevorzugt liegt n im Bereich von 2 bis 6, besonders bevorzugt im Bereich von 2 bis 4. Beispielsweise liegt der Winkel ß bei 90°, 120° oder 180°. In einer weiteren Ausführungsform liegt der Winkel ß im Bereich von 80 bis 100°, im Bereich von 1 10 bis 130° oder im Bereich von 170 bis 190°. In einer weiteren Ausführungsform werden mehr als zwei Fasern (F) in einem Winkel ß zueinander eingebracht, beispielsweise drei oder vier Fasern (F). Diese drei oder vier Fasern (F) können jeweils zu den beiden benachbarten Fasern zwei unterschiedliche Winkel ß, ß-ι und ß2, aufweisen. Bevorzugt weisen alle Fasern (F) zu den beiden benachbarten Fasern (F) die gleichen Winkel auf. Beispielsweise beträgt der Winkel ß 90°, dann beträgt der Winkel ßi zwischen der ersten Faser (F1 ) und der zweiten Faser (F2) 90°, der Winkel ß2 zwischen der zweiten Faser (F2) und dritten Faser (F3) 90°, der Winkel ß3 zwischen der dritten Faser (F3) und der vierten Faser (F4) 90 ° und der Winkel ß4 zwischen der vierten Faser (F4) und der ersten Faser (F1 ) ebenfalls 90 °. Als Winkel ß zwischen der ersten Faser (F1 ) (Referenz) und der zweiten (F2), dritten (F3) und vierten Faser (F4) ergeben sich dann im Uhrzeigersinn 90°, 180° und 270°. Analoge Betrachtungen gelten für die anderen möglichen Winkel. All fibers (F) may be present parallel to each other in the molding. Likewise, it is possible and preferred according to the invention for two or more fibers (F) to be present at an angle β to one another in the shaped body. For the purposes of the present invention, the angle β is the angle between the vertical projection of a first fiber (F1) onto the surface of the first side of the shaped body and the perpendicular projection of a second fiber (F2) onto the surface of the shaped body, both fibers are introduced into the molding. The angle β is preferably in the range β = 360 n, where n is an integer number. Preferably, n is in the range of 2 to 6, more preferably in the range of 2 to 4. For example, the angle β is 90 °, 120 ° or 180 °. In a further embodiment, the angle β is in the range of 80 to 100 °, in the range of 1 10 to 130 ° or in the range of 170 to 190 °. In a further embodiment, more than two fibers (F) are introduced at an angle β to one another, for example three or four fibers (F). These three or four fibers (F) can each be to the two adjacent fibers two different angles ß, ß-ι and ß 2 , have. Preferably, all fibers (F) to the two adjacent fibers (F) at the same angle. For example, the angle β is 90 °, then the angle βi between the first fiber (F1) and the second fiber (F2) is 90 °, the angle β 2 between the second fiber (F2) and third fiber (F3) is 90 °, the angle β 3 between the third fiber (F3) and the fourth fiber (F4) is 90 ° and the angle β 4 between the fourth fiber (F4) and the first fiber (F1) is also 90 °. The angle β between the first fiber (F1) (reference) and the second (F2), third (F3) and fourth fiber (F4) is then 90 ° clockwise, 180 ° and 270 °. Analogous considerations apply to the other possible angles.
Die erste Faser (F1 ) weist dann eine erste Richtung auf, die zweite Faser (F2), die in einem Winkel ß zur ersten Faser (F1 ) angeordnet ist, weist eine zweite Richtung auf. Bevorzugt liegen in der ersten Richtung und der zweiten Richtung eine ähnliche Anzahl von Fasern. Unter „ähnlich" wird vorliegend verstanden, dass der Unterschied zwischen der Anzahl der Fasern in jeder Richtung relativ zu der anderen Richtung < 30 %, besonders bevorzugt < 10 % und insbesondere bevorzugt < 2 % ist. The first fiber (F1) then has a first direction, the second fiber (F2), which is arranged at an angle ß to the first fiber (F1), has a second direction. Preferably, in the first direction and the second direction, a similar number of fibers. By "similar" is meant herein that the difference between the number of fibers in each direction relative to the other direction is <30%, more preferably <10%, and most preferably <2%.
Die Fasern oder Faserbündel können in irregulären oder regulären Mustern eingebracht werden. Bevorzugt ist das Einbringen von Fasern oder Faserbündeln in regulären Mustern. Unter „regulären Mustern" wird im Rahmen der vorliegenden Erfindung verstanden, dass sämtliche Fasern parallel zueinander ausgerichtet sind und dass mindestens eine Faser oder Faserbündel zu allen direkt benachbarten Fasern oder Faserbündeln den gleichen Abstand (a) aufweist. Insbesondere bevorzugt weisen alle Fasern oder Faserbündel zu allen direkt benachbarten Fasern oder Faserbündeln den gleichen Abstand auf. The fibers or fiber bundles can be introduced in irregular or regular patterns. Preference is given to the introduction of fibers or fiber bundles in regular patterns. In the context of the present invention, "regular patterns" are understood to mean that all fibers are aligned parallel to one another and that at least one fiber or fiber bundle has the same distance (a) to all directly adjacent fibers or fiber bundles all the directly adjacent fibers or fiber bundles at the same distance.
In einer weiteren bevorzugten Ausführungsform werden die Fasern oder Faserbündel so eingebracht, dass sie, bezogen auf ein rechtwinkliges Koordinatensystem, bei dem die Dickenrichtung (d) der z-Richtung entspricht, entlang der x-Richtung jeweils zueinander den gleichen Abstand (ax) haben und entlang der y-Richtung den gleichen Abstand (ay). Insbesondere bevorzugt weisen sie in x-Richtung und in y-Richtung den gleichen Abstand (a) auf, wobei a=ax=ay, ist. Liegen zwei oder mehr Fasern (F) in einem Winkel ß zueinander vor, so weisen die ersten Fasern (F1 ), die parallel zueinander vorliegen, vorzugsweise ein reguläres Muster mit einem ersten Abstand (a-ι) auf und die zweiten Fasern (F2), die parallel zueinander vorliegen und in einem Winkel ß zu den ersten Fasern (F1 ) liegen, vorzugsweise ein reguläres Muster mit einem zweiten Abstand (a2). In einer bevorzugten Ausführungsform weisen die ersten Fasern (F1 ) und die zweiten Fasern (F2) jeweils ein reguläres Muster mit einem Abstand (a) auf. Dann gilt a=a-i=a2. Werden Fasern oder Faserbündel mit einem Winkel ß zueinander in den Reaktivschaumstoff eingebracht, so ist es bevorzugt, dass die Fasern oder Faserbündel innerhalb jeder Richtung einem regulären Muster folgen. In a further preferred embodiment, the fibers or fiber bundles are introduced in such a way that, relative to a rectangular coordinate system in which the thickness direction (d) corresponds to the z direction, they have the same distance (a x ) from each other along the x direction and along the y-direction the same spacing (a y). In particular, they have the same distance (a) in the x direction and in the y direction, where a = a x = a y . If two or more fibers (F) are at an angle β to one another, then the first fibers (F1), which are parallel to one another, preferably have a regular pattern with a first spacing (a-1) and the second fibers (F2) which are parallel to each other and are at an angle β to the first fibers (F1), preferably a regular pattern having a second distance (a 2 ). In a preferred embodiment, the first fibers (F1) and the second fibers (F2) each have a regular pattern with a spacing (a). Then a = ai = a 2 . If fibers or fiber bundles are introduced into the reactive foam at an angle β to one another, it is preferred that the fibers or fiber bundles follow a regular pattern within each direction.
In einer bevorzugten Ausführungsform des Formkörpers gemäß der vorliegenden Erfindung i) weist die Oberfläche von mindestens einer Seite des Formkörpers mindestens eine Vertiefung auf, vorzugsweise ist die Vertiefung ein Schlitz oder ein Loch, mehr bevorzugt wird mindestens eine Vertiefung auf der Oberfläche von mindestens einer Seite des Formkörpers im Anschluss an die Durchführung von Schritt IV) des Formschäumverfahrens erzeugt, und/oder ii) ist die Gesamtoberfläche des Formkörpers zu mehr als 30 %, vorzugsweise zu mehr als 50 %, mehr bevorzugt zu mehr als 80 %, insbesondere zu mehr als 95 %, geschlossen. In a preferred embodiment of the shaped body according to the present invention i) the surface of at least one side of the shaped body has at least one recess, preferably the recess is a slot or a hole, more preferably at least one recess on the surface of at least one side of the Formed body after the implementation of step IV) of the foam molding process, and / or ii) the total surface area of the shaped body to more than 30%, preferably more than 50%, more preferably more than 80%, in particular more than 95 %, closed.
Figur 1 zeigt eine schematische Darstellung einer bevorzugten Ausführungsform des erfindungsgemäßen Formkörpers aus Reaktivschaumstoff (1 ) in einer perspektivischen Ansicht. (2) stellt dabei (die Oberfläche) einer ersten Seite des Formkörpers dar, während (3) eine zweite Seite des entsprechenden Formkörpers darstellt. Wie aus Figur 1 weiterhin ersichtlich, liegt die erste Seite (2) des Formkörpers gegenüber der zweiten Seite (3) dieses Formkörpers. Die Faser (F) ist durch (4) dargestellt. Ein Ende dieser Faser (4a) und somit der Faserbereich (FB1 ) ragt aus der ersten Seite (2) des Formkörpers heraus, während das andere Ende (4b) der Faser, das den Faserbereich (FB3) darstellt, aus der zweiten Seite (3) des Formkörpers herausragt. Der mittlere Faserbereich (FB2) befindet sich innerhalb des Formkörpers und ist somit von dem Reaktivschaumstoff umschlossen. FIG. 1 shows a schematic representation of a preferred embodiment of the shaped body of reactive foam (1) according to the invention in a perspective view. (2) represents (the surface) of a first side of the molding, while (3) represents a second side of the corresponding molding. As can also be seen from FIG. 1, the first side (2) of the shaped body lies opposite the second side (3) of this shaped body. The fiber (F) is represented by (4). One end of this fiber (4a) and thus the fiber portion (FB1) protrude from the first side (2) of the shaped body, while the other end (4b) of the fiber, which represents the fiber portion (FB3), from the second side (3 ) protrudes the molding. The middle fiber region (FB2) is located within the molding and is thus enclosed by the reactive foam.
In Figur 1 befindet sich die Faser (4), die beispielsweise eine einzelne Faser oder ein Faserbündel, vorzugsweise ein Faserbündel, ist, in einem Winkel α relativ zu Dickenrichtung (d) des Formkörpers bzw. zur Orthogonalen (der Oberfläche) der ersten Seite (2) des Formkörpers. Der Winkel α beträgt 10 bis 70°, vorzugsweise 30 bis 60°, besonders bevorzugt 30 bis 50°, ganz besonders 30 bis 45°, insbesondere 45°. In Figur 1 ist der Übersichtlichkeit halber nur eine einzelne Faser (F) dargestellt. In FIG. 1, the fiber (4), which is for example a single fiber or a fiber bundle, preferably a fiber bundle, is at an angle α relative to the thickness direction (d) of the shaped body or to the orthogonal (the surface) of the first side (FIG. 2) of the molding. The angle α is 10 to 70 °, preferably 30 to 60 °, particularly preferably 30 to 50 °, especially 30 to 45 °, in particular 45 °. For the sake of clarity, only a single fiber (F) is shown in FIG.
Figur 3 zeigt beispielhaft eine schematische Darstellung eines Teils der verschiedenen Winkel. Der in Figur 3 dargestellte Formkörper aus Reaktivschaumstoff (1 ) enthält eine erste Faser (41 ) und eine zweite Faser (42). In Figur 3 ist zur besseren Übersichtlichkeit lediglich der Faserbereich (FB1 ), der aus der ersten Seite (2) des Formkörpers herausragt, für die beiden Fasern (41 ) und (42) eingezeichnet. Die erste Faser (41 ) bildet relativ zur Orthogonalen (O) der Oberfläche der ersten Seite (2) des Formkörpers einen ersten Winkel α (α1 ). Die zweite Faser (42) bildet relativ zur Orthogonalen (O) der Oberfläche der ersten Seite (2) einen zweiten Winkel α (α2). Die senkrechte Projektion der ersten Faser (41 ) auf die erste Seite (2) des Formkörpers (41 p) bildet mit der senkrechten Projektion der zweiten Faser (42) auf die erste Seite (2) des Formkörpers (42p) den Winkel ß. FIG. 3 shows, by way of example, a schematic representation of part of the various angles. The shaped body of reactive foam (1) shown in FIG. 3 contains a first fiber (41) and a second fiber (42). In FIG. 3, for the sake of clarity, only the fiber region (FB1), which consists of the first side (2) of FIG Shaped protruding body, drawn for the two fibers (41) and (42). The first fiber (41) forms a first angle α (α1) relative to the orthogonal (O) of the surface of the first side (2) of the shaped body. The second fiber (42) forms a second angle α (α2) relative to the orthogonal (O) of the surface of the first side (2). The perpendicular projection of the first fiber (41) onto the first side (2) of the shaped body (41 p) forms the angle β with the perpendicular projection of the second fiber (42) onto the first side (2) of the shaped body (42 p).
Der im Formkörper enthaltene Reaktivschaumstoff wird nach einem Formschäumverfahren hergestellt. The reactive foam contained in the molded body is produced by a foam molding process.
Formschäumverfahren sind dem Fachmann als solche bekannt. Vorzugsweise umfasst das Formschäumverfahren die folgenden Schritte I) bis IV). I) Bereitstellung einer reaktiven Mischung, die zumindest eine erste Komponente (K1 ) und eine zweite Komponente (K2) enthält, wobei die erste Komponente (K1 ) und die zweite Komponente (K2) miteinander reagieren können, II) Injektion der in Schritt I) bereitgestellten reaktiven Mischung in ein formgebendes Werkzeug, Shaped foam processes are known to the person skilled in the art. Preferably, the foam molding process comprises the following steps I) to IV). I) providing a reactive mixture containing at least a first component (K1) and a second component (K2), wherein the first component (K1) and the second component (K2) can react with each other, II) injection of the in step I) provided reactive mixture into a shaping tool,
II I) Expansion der reaktiven Mischung in dem formgebenden Werkzeug unter Erhalt eines expandierten Schaumstoffs und II I) expansion of the reactive mixture in the forming tool to obtain an expanded foam and
IV) Entformen des in Schritt II I) erhaltenen expandierten Schaumstoffs aus dem formgebenden Werkzeug unter Erhalt des Reaktivschaumstoffs. IV) demolding of the expanded foam obtained in step II I) from the forming tool to obtain the reactive foam.
Als erste Komponente (K1 ) und zweite Komponente (K2), die in der in Schritt I) bereitgestellten reaktiven Mischung enthalten sind, eignen sich sämtliche erste Komponenten (K1 ) und zweite Komponenten (K2), die miteinander reagieren können. Derartige Komponenten sind dem Fachmann als solche bekannt. As the first component (K1) and second component (K2) contained in the reactive mixture provided in step I), all the first components (K1) and second components (K2) which are capable of reacting with each other are suitable. Such components are known in the art as such.
Als erste Komponente (K1 ) eignen sich beispielsweise Isocyanate. Isocyanate als solche sind dem Fachmann bekannt. Im Rahmen der vorliegenden Erfindung werden unter Isocyanaten alle aliphatischen, cycloaliphatischen und aromatischen Di- und/oder Polyisocyanate verstanden. Aromatische Di- und/oder Polyisocyanate sind bevorzugt. Besonders bevorzugt als erste Komponente (K1 ) sind Toluoldiisocyanat (TDI), Diphenylmethandiisocyanat (MDI), polymere Diphenylmethandiisocyanate (PMDI) und Mischungen daraus. Insbesondere bevorzugt sind Mischungen aus Diphenylmethandiisocyanat (MDI) und polymere Diphenylmethandiisocyanate (PMDI) als erste Komponente (K1 ). As the first component (K1), for example, isocyanates are suitable. Isocyanates as such are known to the person skilled in the art. In the context of the present invention, isocyanates are understood as meaning all aliphatic, cycloaliphatic and aromatic di- and / or polyisocyanates. Aromatic di- and / or polyisocyanates are preferred. Particularly preferred as the first component (K1) are toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polymeric diphenylmethane diisocyanates (PMDI) and mixtures thereof. Especially preferred are mixtures of diphenylmethane diisocyanate (MDI) and polymeric diphenylmethane diisocyanates (PMDI) as the first component (K1).
Werden als erste Komponente (K1 ) Isocyanate eingesetzt, so können diese ganz oder 5 teilweise mit Uretdion-, Carbamat-, Isocyanurat-, Carbodiimid-, Allophanat- und/oder Urethangruppen modifiziert sein. Bevorzugt sind sie mit Urethangruppen modifiziert. Derartige Isocyanate sind dem Fachmann als solche bekannt. If isocyanates are used as the first component (K1), these may be modified in whole or in part with uretdione, carbamate, isocyanurate, carbodiimide, allophanate and / or urethane groups. Preferably, they are modified with urethane groups. Such isocyanates are known in the art as such.
Als Isocyanate eignen sich zudem Präpolymere sowie Mischungen aus den oben 10 beschriebenen Isocyanaten und Präpolymeren. Die Präpolymere werden aus den oben beschriebenen Isocyanaten sowie den weiter unten beschriebenen Polyethern, Polyestern oder Mischungen daraus, hergestellt. Also suitable as isocyanates are prepolymers and mixtures of the isocyanates and prepolymers described above. The prepolymers are prepared from the isocyanates described above and the polyethers, polyesters or mixtures thereof described below.
Als erste Komponente (K1 ) geeignete Isocyanate weisen bevorzugt einen 15 Isocyanatindex im Bereich von 100 bis 400, besonders bevorzugt im Bereich von 100 bis 300, insbesondere bevorzugt im Bereich von 100 bis 200, auf. Isocyanates suitable as first component (K1) preferably have an isocyanate index in the range from 100 to 400, particularly preferably in the range from 100 to 300, particularly preferably in the range from 100 to 200.
Unter dem Isocyanatindex wird im Rahmen der vorliegenden Erfindung das stöchiometrische Verhältnis an Isocyanatgruppen zu mit Isocyanat reaktiven Gruppen, 20 multipliziert mit 100, verstanden. Unter mit Isocyanat reaktiven Gruppen werden dabei alle in der reaktiven Mischung enthaltenen, gegenüber Isocyanat reaktiven Gruppen, einschließlich gegebenenfalls chemischer Treibmittel und Verbindungen mit Epoxidgruppen, verstanden, nicht aber die Isocyanatgruppe selbst. In the context of the present invention, the isocyanate index is understood as meaning the stoichiometric ratio of isocyanate groups to isocyanate-reactive groups, 20 multiplied by 100. Isocyanate-reactive groups are understood to mean all isocyanate-reactive groups present in the reactive mixture, including, if appropriate, chemical blowing agents and compounds containing epoxide groups, but not the isocyanate group itself.
25 Als zweite Komponente (K2) wird bevorzugt mindestens eine Verbindung mit gegenüber Isocyanaten reaktiven Gruppen, eingesetzt. Derartige Verbindungen sind dem Fachmann bekannt. The second component (K2) used is preferably at least one compound containing isocyanate-reactive groups. Such compounds are known to the person skilled in the art.
Als Verbindung mit gegenüber Isocyanaten reaktiven Gruppen können beispielsweise 30 alle Verbindungen eingesetzt werden, die zumindest zwei gegenüber Isocyanaten reaktiven Gruppen, wie OH-, SH-, N H- und/oder CH-azide Gruppen aufweisen. For example, all compounds which have at least two isocyanate-reactive groups, such as OH, SH, N H and / or CH-azide groups, can be used as compound with isocyanate-reactive groups.
Bevorzugt als zweite Komponente (K2) ist eine Verbindung mit gegenüber Isocyanaten reaktiven Gruppen, die ausgewählt ist aus der Gruppe bestehend ausPreferred as a second component (K2) is a compound having isocyanate-reactive groups which is selected from the group consisting of
35 Polyetherpolyolen, Polyesterpolyolen und Polyaminen, wobei die mindestens eine Verbindung mit gegenüber Isocyanaten reaktiven Gruppen eine Funktionalität von 2 bis 8 aufweist und wobei, wenn die zweite Komponente (K2) ausgewählt ist aus Polyetherpolyolen und Polyesterpolyolen, die mindestens eine Verbindung mit gegenüber Isocyanaten reaktiven Gruppen eine mittlere Hydroxylzahl von35 polyether polyols, polyester polyols and polyamines, wherein the at least one compound having isocyanate-reactive groups having a functionality of 2 to 8 and wherein, when the second component (K2) is selected from polyether polyols and polyester polyols containing at least one compound with isocyanate-reactive groups an average hydroxyl number of
40 12 bis 1200 mg KOH/g aufweist. Polyetherpolyole als solche sind dem Fachmann bekannt und können nach bekannten Verfahren hergestellt werden, beispielsweise durch anionische Polymerisation von Alkylenoxiden unter Zusatz mindestens eines Startermoleküls, das vorzugsweise 2 bis 6 reaktive Wasserstoffatome gebunden enthält, in Gegenwart von Katalysatoren. Als Katalysatoren können Alkalihydroxide wie beispielsweise Natrium- oder Kaliumhydroxid oder Alkalialkoholate wie Natriummethylat, Natrium- oder Kaliumethylat oder Kaliumisopropylat eingesetzt werden. Bei kationischer Polymerisation werden als Katalysatoren beispielsweise Lewis-Säuren wie Ammoniumpentachlorid, Bortriflurid-Etherat oder Bleicherde eingesetzt. Weiter können als Katalysatoren auch Doppelmetallcyanidverbindungen, sogenannte DMC-Katalysatoren, sowie amin- basierte Katalysatoren eingesetzt werden. 40 12 to 1200 mg KOH / g. Polyether polyols as such are known to the person skilled in the art and can be prepared by known processes, for example by anionic polymerization of alkylene oxides with the addition of at least one starter molecule which preferably contains 2 to 6 bonded reactive hydrogen atoms, in the presence of catalysts. As catalysts, alkali metal hydroxides such as sodium or potassium hydroxide or alkali metal such as sodium, sodium or potassium or potassium are used. In the case of cationic polymerization, the catalysts used are, for example, Lewis acids such as ammonium pentachloride, boron trifluoride etherate or bleaching earth. Furthermore, as catalysts it is also possible to use double metal cyanide compounds, so-called DMC catalysts, and amine-based catalysts.
Vorzugsweise werden als Alkylenoxide eine oder mehrere Verbindungen mit zwei bis vier Kohlenstoffatomen im Alkylenrest wie beispielsweise Ethylenoxid, Tetra h yd rofu ran, 1 ,2-Propylenoxid, 1 ,3-Propylenoxid, 1 ,2-Butylenoxid, 2,3-Butylenoxid sowie Mischungen daraus, eingesetzt. Bevorzugt werden Ethylenoxid und/oder 1 ,2- Propylenoxid eingesetzt. Preferably, as alkylene oxides, one or more compounds having two to four carbon atoms in the alkylene radical such as ethylene oxide, Tetra h yd rofu ran, 1, 2-propylene oxide, 1, 3-propylene oxide, 1, 2-butylene oxide, 2,3-butylene oxide and mixtures from it, used. Preference is given to using ethylene oxide and / or 1,2-propylene oxide.
Als Startermoleküle kommen beispielsweise Ethylenglycol, Diethylenglycol, Propylenglycol, Dipropylenglycol, Glyzerin, Trimethylolpropan, Pentaerythrit, Zuckerderivate wie Saccharose, Hexitderivate wie Sorbit, Methylamin, Ethylamin, Isopropylamin, Butylamin, Benzylamin, Anilin, Toluidin, Toluoldiamin, Naphtylamin, Ethylendiamin, Diethylentriamin, 4,4'-Methylendianilin, 1 ,3-Propandiamin, 1 ,6-Hexandiamin, Ethanolamin, Diethanolamin, Triethanolamin sowie andere dem Fachmann bekannte zwei- oder mehrwertige Alkohole oder ein- oder mehrwertige Amine in Betracht. Examples of starter molecules are ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerol, trimethylolpropane, pentaerythritol, sugar derivatives such as sucrose, hexitol derivatives such as sorbitol, methylamine, ethylamine, isopropylamine, butylamine, benzylamine, aniline, toluidine, toluenediamine, naphthylamine, ethylenediamine, diethylenetriamine, 4 4'-methylenedianiline, 1, 3-propanediamine, 1, 6-hexanediamine, ethanolamine, diethanolamine, triethanolamine and other known to those skilled di- or polyhydric alcohols or mono- or polyhydric amines into consideration.
Als Polyesterpolyole eignen sich alle dem Fachmann bekannten Polyesterpolyole. Beispielsweise können geeignete Polyesterpolyole durch Kondensation von mehrfunktionellen Alkoholen mit zwei bis zwölf Kohlenstoffen wie Ethylenglycol, Diethylenglycol, Butandiol, Trimethylolpropan, Glyzerin oder Pentaerythrit, mit mehrfunktionellen Carbonsäuren mit zwei bis zwölf Kohlenstoffatomen, beispielsweise Bernsteinsäure, Glutarsäure, Adipinsäure, Korksäure, Azelainsäure, Sebacinsäure, Decandicarbonsäure, Maleinsäure, Fumarsäure, Phthalsäure, Isophthalsäure, Terephthalsäure, den Isomeren von Naphthalindicarbonsäuren, den Anhydriden der genannten Säuren sowie Mischungen daraus, hergestellt. Bevorzugt werden aromatische Disäuren wie Phthalsäure, Isophthalsäure und/oder Terephthalsäure sowie deren Anhydride als Säurekomponente und Ethylenglycol, Diethylenglycol, 1 ,4-Butandiol und/oder Glyzerin als Alkoholkomponente eingesetzt. Darüber hinaus können zur Herstellung der Polyesterpolyole anstatt der mehrfunktionellen Carbonsäuren auch entsprechende monomere Ester wie z.B. Dimethylterephthalat oder polymere Ester wie z.B. Polyethylenterephthalat, eingesetzt werden. Suitable polyester polyols are all polyester polyols known to those skilled in the art. For example, suitable polyester polyols may be prepared by condensing polyhydric alcohols of two to twelve carbons such as ethylene glycol, diethylene glycol, butanediol, trimethylolpropane, glycerol or pentaerythritol with polyfunctional carboxylic acids having two to twelve carbon atoms, for example, succinic, glutaric, adipic, suberic, azelaic, sebacic, decanedicarboxylic , Maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, the isomers of naphthalenedicarboxylic acids, the anhydrides of said acids, and mixtures thereof. Preference is given to using aromatic diacids such as phthalic acid, isophthalic acid and / or terephthalic acid and their anhydrides as the acid component and ethylene glycol, diethylene glycol, 1,4-butanediol and / or glycerol as the alcohol component. In addition, instead of the polyfunctional carboxylic acids and corresponding monomeric esters such as dimethyl terephthalate or polymeric esters such as polyethylene terephthalate can be used to prepare the polyester.
Als Polyamine eignen sich alle dem Fachmann bekannten Polyamine. Geeignete Polyamine sind sowohl aliphatische Polyamine als auch aromatische Polyamine. Bevorzugt sind aliphatische Polyamine, die im Rahmen der vorliegenden Erfindung auch als Polyalkylenpolyamine bezeichnet werden. Suitable polyamines are all polyamines known to the person skilled in the art. Suitable polyamines are both aliphatic polyamines and aromatic polyamines. Preference is given to aliphatic polyamines, which are also referred to as polyalkylenepolyamines in the context of the present invention.
Unter dem Begriff „Polyalkylenpolyamin" werden im Rahmen der vorliegenden Erfindung aliphatische Amine verstanden, die mindestens drei Aminogruppen (primär, sekundär oder tertiär) enthalten. Als Polyalkylenpolyamine sind Polyethylenimine besonders bevorzugt. Unter „Polyethyleniminen" werden im Rahmen der vorliegenden Erfindung sowohl oligomere als auch Homo- und Copolymere verstanden, welche die Gruppierungen -CH2-CH2- NH- aufweisen und mindestens drei Aminogruppen enthalten. Die erste Komponente (K1 ) und die zweite Komponente (K2) können miteinander reagieren. Diese Reaktionen sind dem Fachmann als solche bekannt. For the purposes of the present invention, the term "polyalkylenepolyamine" is understood as meaning aliphatic amines containing at least three amino groups (primary, secondary or tertiary) .Polyethylene polyethylenes are particularly preferably polyethylenimines Homopolymers and copolymers understood which have the groupings -CH 2 -CH 2 -NH- and contain at least three amino groups. The first component (K1) and the second component (K2) can react with each other. These reactions are known to those skilled in the art.
Bei der Reaktion der ersten Komponente (K1 ) mit der zweiten Komponente (K2) bilden sich beispielsweise Polyurethane, Polyisocyanurate oder Polyharnstoffe, bevorzugt bilden sich Polyisocyanate oder Polyurethane, am meisten bevorzugt bilden sich Polyurethane. Dem Fachmann sind diese Reaktionen bekannt. In the reaction of the first component (K1) with the second component (K2), for example, form polyurethanes, polyisocyanurates or polyureas, preferably form polyisocyanates or polyurethanes, most preferably form polyurethanes. The person skilled in these reactions are known.
Beispielsweise bilden sich Polyurethane, wenn als erste Komponente (K1 ) Isocyanate eingesetzt werden und als zweite Komponente (K2) Polyetherpolyole. Polyisocyanurate bilden sich bei dem Einsatz von Isocyanaten als erste Komponente (K1 ) und Polyesterpolyolen als zweite Komponente (K2). Polyharnstoffe werden erhalten durch die Reaktion von Isocyanaten als erste Komponente (K1 ) und Polyaminen als zweite Komponente (K2). Es versteht sich von selbst, dass Polyurethane auch beispielsweise Isocyanurateinheiten, Allophanateinheiten, Harnstoffeinheiten, Carbodiimideinheiten, Biureteinheiten, Uretonimineinheiten sowie gegebenenfalls weitere Einheiten, die sich bei Additionsreaktionen von Isocyanaten als erste Komponente (K1 ) bilden können, enthalten können. Entsprechend können Polyisocyanurate beispielsweise auch Urethaneinheiten, Allophanateinheiten, Harnstoffeinheiten, Carbodiimideinheiten, Biureteinheiten, Uretonimineinheiten sowie gegebenenfalls weitere Einheiten, die sich bei Additionsreaktionen von Isocyanaten als erste Komponente (K1 ) bilden können, enthalten. Ebenso können Polyharnstoffe beispielsweise auch Isocyanurateinheiten, Allophanateinheiten, Urethaneinheiten, Carbodiimideinheiten, Biureteinheiten, Uretonimineinheiten sowie gegebenenfalls weitere Einheiten, die sich bei Additionsreaktionen von Isocyanaten als erste Komponente (K1 ) bilden können, enthalten. For example, polyurethanes are formed when isocyanates are used as the first component (K1) and polyether polyols as the second component (K2). Polyisocyanurates are formed in the use of isocyanates as the first component (K1) and polyester polyols as the second component (K2). Polyureas are obtained by the reaction of isocyanates as the first component (K1) and polyamines as the second component (K2). It goes without saying that polyurethanes may also contain, for example, isocyanurate units, allophanate units, urea units, carbodiimide units, biuret units, uretonimine units and optionally further units which may form as addition reaction of isocyanates as first component (K1). Accordingly, polyisocyanurates may, for example, also urethane units, allophanate units, urea units, carbodiimide units, biuret units, uretonimine units and optionally further units which may be in addition reactions of isocyanates as the first component (K1) can form included. Likewise, polyureas, for example, can also contain isocyanurate units, allophanate units, urethane units, carbodiimide units, biuret units, uretonimine units and optionally further units which can form as addition reaction of isocyanates as first component (K1).
Die Bereitstellung der reaktiven Mischung in Schritt I) kann nach allen dem Fachmann bekannten Methoden erfolgen. The provision of the reactive mixture in step I) can be carried out by all methods known to the person skilled in the art.
Zur Bereitstellung der reaktiven Mischung werden die erste Komponente (K1 ) und die zweite Komponente (K2) sowie die gegebenenfalls in der reaktiven Mischung enthaltenen weiteren Komponenten und/oder Katalysatoren und/oder weiteren Additive üblicherweise gemischt. Das Mischen erfolgt beispielsweise bei einer Temperatur im Bereich von 15 bis 130 °C, bevorzugt im Bereich von 15 bis 90 °C, insbesondere bevorzugt im Bereich von 25 bis 55 °C. To provide the reactive mixture, the first component (K1) and the second component (K2) as well as the optional further components and / or catalysts and / or further additives contained in the reactive mixture are usually mixed. The mixing takes place for example at a temperature in the range of 15 to 130 ° C, preferably in the range of 15 to 90 ° C, particularly preferably in the range of 25 to 55 ° C.
Das Mischen kann nach allen dem Fachmann bekannten Methoden erfolgen, beispielsweise mechanisch mittels eines Rührers oder einer Rührschnecke oder unter hohem Druck in einem Gegenstrominjektionsverfahren. The mixing can be carried out by all methods known to the person skilled in the art, for example mechanically by means of a stirrer or a stirring screw or under high pressure in a countercurrent injection method.
Die in Schritt I) bereitgestellte reaktive Mischung kann zudem noch weitere Komponenten enthalten. Weitere Komponenten sind beispielsweise physikalische und/oder chemische Treibmittel. The reactive mixture provided in step I) may also contain further components. Other components include physical and / or chemical blowing agents.
Unter chemischen Treibmitteln werden im Rahmen der vorliegenden Erfindung Treibmittel verstanden, die zunächst in fester oder flüssiger Form in der reaktiven Mischung enthalten sind und dann durch chemische Reaktion mit den Komponenten (K1 ) und/oder (K2), sowie gegebenenfalls mit weiteren in der reaktiven Mischung enthaltenen Komponenten reagieren, wobei sich gasförmige Produkte bilden, die dann als eigentliches Treibmittel dienen. In the context of the present invention, chemical blowing agents are understood to mean blowing agents which are initially present in solid or liquid form in the reactive mixture and then by chemical reaction with the components (K1) and / or (K2), and optionally with others in the reactive one Mix containing components react, forming gaseous products, which then serve as the actual propellant.
Unter physikalischen Treibmitteln werden im Rahmen der vorliegenden Erfindung Treibmittel verstanden, die in der reaktiven Mischung gegebenenfalls unter Druck, gelöst oder emulgiert sind und unter den Bedingungen, bei denen die reaktive Mischung reagiert, verdampfen. In the context of the present invention, physical blowing agents are understood to mean blowing agents which, if appropriate under pressure, are dissolved or emulsified in the reactive mixture and evaporate under the conditions in which the reactive mixture reacts.
Geeignete chemische und physikalische Treibmittel sind dem Fachmann als solche bekannt. Zu den chemischen Treibmitteln zählen beispielsweise Wasser und Carbonsäuren, insbesondere Ameisensäure. Suitable chemical and physical blowing agents are known to those skilled in the art. The chemical blowing agents include, for example, water and carboxylic acids, especially formic acid.
Zu den physikalischen Treibmitteln zählen beispielsweise Kohlenwasserstoffe, insbesondere (cyclo)aliphatische Kohlenwasserstoffe, halogenierte Kohlenwasserstoffe, wie perfluorierte Alkane, Pentafluorhexan, Fluorchlorkohlenwasserstoffe, Etheresterketone und Acetale, sowie anorganische und organische Verbindungen, die beim Erhitzen Stickstoff freisetzen. Ebenso können Mischungen aus den genannten physikalischen Treibmitteln eingesetzt werden, beispielsweise aus (cyclo)aliphatischen Kohlenwasserstoffen mit 4 bis 8 Kohlenstoffatomen oder aus Fluorkohlenwasserstoffen, wie 1 , 1 , 1 ,3,3- Pentafluoropropan (HFC 245 fa), Trifluormethan, Difluormethan, 1 , 1 , 1 ,3,3- Pentafluorbutan (H FC 365 mfc), 1 , 1 , 1 ,2-Tetrafluorethan, Difluorethan und Heptafluorpropan. Zudem sind Kombinationen mit chemischen Treibmitteln möglich. The physical blowing agents include, for example, hydrocarbons, in particular (cyclo) aliphatic hydrocarbons, halogenated hydrocarbons such as perfluorinated alkanes, pentafluorohexane, chlorofluorocarbons, Etheresterketone and acetals, and inorganic and organic compounds that release nitrogen when heated. It is likewise possible to use mixtures of the abovementioned physical blowing agents, for example of (cyclo) aliphatic hydrocarbons having 4 to 8 carbon atoms or of fluorohydrocarbons, such as 1,1,3,3,3-pentafluoropropane (HFC 245 fa), trifluoromethane, difluoromethane, 1 , 1, 1, 3,3-pentafluorobutane (H FC 365 mfc), 1, 1, 1, 2-tetrafluoroethane, difluoroethane and heptafluoropropane. In addition, combinations with chemical blowing agents are possible.
Bevorzugte (cyclo)aliphatische Kohlenwasserstoffe mit 4 bis 8 Kohlenstoffatomen sind beispielsweise n-Pentan, iso-Pentan und Cyclopentan. Preferred (cyclo) aliphatic hydrocarbons having 4 to 8 carbon atoms are, for example, n-pentane, iso-pentane and cyclopentane.
Bevorzugt ist das Treibmittel der reaktiven Mischung ausgewählt aus der Gruppe bestehend aus n-Pentan, Iso-Pentan, Cyclopentan, 1 , 1 ,1 ,3,3-Pentafluorbutan, 1 , 1 , 1 ,3,3-Pentafluoropropan, 1 , 1 , 1 ,2,3,3,3-Heptafluoropropan, Wasser, Ameisensäure und Hydrofluoroolefinen, wie 1 ,1 , 1 ,4,4,4 hexafluoro-2-butene und 1 -chloro-3,3,3- trifluoro-propene. Weiterhin bevorzugt enthält das Treibmittel Wasser, insbesondere bevorzugt besteht das Treibmittel aus Wasser. Preferably, the propellant of the reactive mixture is selected from the group consisting of n-pentane, iso-pentane, cyclopentane, 1,1,1,3,3-pentafluorobutane, 1,1,1,3,3-pentafluoropropane, 1,1 , 1, 2,3,3,3-heptafluoropropane, water, formic acid and hydrofluoroolefins, such as 1,1,1,4,4,4-hexafluoro-2-butenes and 1-chloro-3,3,3-trifluoro-propenes , Further preferably, the propellant contains water, more preferably the propellant is water.
Zudem kann die reaktive Mischung Katalysatoren enthalten. Als Katalysatoren können alle Verbindungen eingesetzt werden, die die Reaktion der ersten Komponente (K1 ) mit der zweiten Komponente (K2) beschleunigen. Solche Verbindungen sind bekannt und beispielsweise im„Kunststoffhandbuch Band 7, Polyurethan, Karl Hanser Verlag, 3. Auflage 1993, Kapitel 3.4.1 " beschrieben. In addition, the reactive mixture may contain catalysts. As catalysts, it is possible to use all compounds which accelerate the reaction of the first component (K1) with the second component (K2). Such compounds are known and described for example in "Kunststoffhandbuch Volume 7, polyurethane, Karl Hanser Verlag, 3rd edition 1993, chapter 3.4.1".
Darüber hinaus kann die in Schritt I) bereitgestellte reaktive Mischung weitere Additive enthalten. Derartige Additive sind dem Fachmann als solche bekannt. Additive sind beispielsweise Stabilisatoren, grenzflächenaktive Substanzen, Flammschutzmittel und Kettenverlängerer. In addition, the reactive mixture provided in step I) may contain further additives. Such additives are known in the art as such. Additives are, for example, stabilizers, surface-active substances, flame retardants and chain extenders.
Stabilisatoren werden auch als Schaumstabilisatoren bezeichnet. Unter Stabilisatoren werden im Rahmen der vorliegenden Erfindung Stoffe verstanden, welche die Ausbildung einer regelmäßigen Zellstruktur bei der Schaumbildung fördern. Geeignete Stabilisatoren sind beispielsweise silikonhaltige Schaumstabilisatoren wie Siloxan-Oxalkylen-Mischpolymerisate und andere Organopolysiloxane, ferner Alkoxylierungsprodukte von Fettalkoholen, Oxoalkoholen, Fettaminen, Alkylphenolen, Dialkylphenolen, Alkylkresolen, Alkylresorcin, Naphthol, Alkylnaphthol, Naphtylamin, Anilin, Alkylanilin, Tolouidin, Bisphenol A, alkyliertem Bisphenol A, Polyvinylalkohol sowie weitere Alkoxylierungsprodukte von Kondensationsprodukten aus Formaldehyd und Alkylphenolen, Formaldehyd und Dialkylphenolen, Formaldehyd und Alkylkresolen, Formaldehyd und Alkylresorcin, Formaldehyd und Anilin, Formaldehyd und Tolouidin, Formaldehyd und Naphthol, Formaldehyd und Alkylnaphthol sowie Formaldehyd und Bisphenol A oder Mischungen aus zwei oder mehrere dieser Schaumstabilisatoren. Stabilizers are also referred to as foam stabilizers. In the context of the present invention, stabilizers are understood to be substances which promote the formation of a regular cell structure during foam formation. suitable Stabilizers are, for example, silicone-containing foam stabilizers such as siloxane-oxalkylene copolymers and other organopolysiloxanes, and also alkoxylation products of fatty alcohols, oxoalcohols, fatty amines, alkylphenols, dialkylphenols, alkylcresols, alkylresorcinol, naphthol, alkylnaphthol, naphthylamine, aniline, alkylaniline, toluidine, bisphenol A, alkylated bisphenol A , Polyvinyl alcohol and other alkoxylation of condensation products of formaldehyde and alkylphenols, formaldehyde and dialkylphenols, formaldehyde and alkylcresols, formaldehyde and alkylresorcinol, formaldehyde and aniline, formaldehyde and toluidine, formaldehyde and naphthol, formaldehyde and alkylnaphthol and formaldehyde and bisphenol A or mixtures of two or more of these foam stabilizers.
Grenzflächenaktive Substanzen werden auch als oberflächenaktive Substanzen bezeichnet. Unter grenzflächenaktiven Substanzen werden Verbindungen verstanden, welche zur Unterstützung der Homogenisierung der Ausgangsstoffe dienen und gegebenenfalls auch geeignet sind, die Zellstruktur der Kunststoffe zu regulieren. Dazu zählen beispielsweise Emulgatoren wie Natriumsalze von Rizinusölsulfaten oder von Fettsäuren sowie Salze von Fettsäuren mit Aminen, z.B. ölsaures Diethylamin, stearinsaures Diethanolamin, rizinolsaures Diethanolamin, Salze von Sulfonsäuren, z.B. Alkali- oder Ammoniumsalze von Dodecylbenzoldisulfonsäure, Dinaphtylmethandisulfonsäure und Rizinolsäure. Surface-active substances are also referred to as surface-active substances. Surface-active substances are compounds which serve to assist the homogenization of the starting materials and, if appropriate, are also suitable for regulating the cell structure of the plastics. These include, for example, emulsifiers such as sodium salts of castor oil sulfates or of fatty acids and salts of fatty acids with amines, e.g. diethylamine oleate, diethanolamine stearate, diethanolamine ricinoleic acid, salts of sulfonic acids, e.g. Alkali or ammonium salts of dodecylbenzene disulfonic acid, dinaphthylmethanedisulfonic acid and ricinoleic acid.
Als Flammschutzmittel können beispielsweise organische Phosphorsäure- und/oder Phosphonsäureester eingesetzt werden. Vorzugsweise werden gegenüber Isocyanatgruppen nicht-reaktive Verbindungen eingesetzt. Auch Chlor-enthaltende Phosphorsäureester gehören zu den bevorzugten Verbindungen. Geeignete Flammschutzmittel sind beispielsweise Tris-(2-chlorpropyl)phosphat, Triethylphosphat, Diphenylkresylphosphat, Diethylethanphosphinat, Trikresylphosphat, Tris-(2- chlorethyl)-phosphat, Tris-(1 ,3-dichlorpropyl)-phosphat, Tris-(2,3- dibrompropopyl)-phosphat, Tetrakis-(2-chlorethyl)-ethylendiphosphat, Dimethylmethanphosphonat, Diethanolaminomethylphosphonsäure-Diethylester sowie handelsübliche halogenierte Flammschutzpolyole. As flame retardants, for example, organic phosphoric acid and / or phosphonic acid esters can be used. Preference is given to using non-reactive compounds over isocyanate groups. Chlorine-containing phosphoric acid esters are also among the preferred compounds. Suitable flame retardants are, for example, tris (2-chloropropyl) phosphate, triethyl phosphate, diphenyl cresyl phosphate, diethyl ethane phosphinate, tricresyl phosphate, tris (2-chloroethyl) phosphate, tris (1,3-dichloropropyl) phosphate, tris- (2,3-) dibromopropyl) phosphate, tetrakis- (2-chloroethyl) ethylenediphosphate, dimethylmethanephosphonate, diethanolaminomethylphosphonic acid diethyl ester and commercially available halogenated flame retardant polyols.
Daneben können beispielsweise auch Brom-enthaltende Flammschutzmittel zum Einsatz kommen. Als Brom-enthaltende Flammschutzmittel werden vorzugsweise Verbindungen eingesetzt, die gegenüber der Isocyanatgruppe reaktiv sind. Derartige Verbindungen sind beispielsweise Ester der Tetrabromphthalsäure mit aliphatischen Diolen und Alkoxylierungsprodukte des Dibrombutendiols. Auch Verbindungen, die sich aus der Reihe der bromierten, OH-Gruppen enthaltenden Neopentylverbindungen ableiten, können zur Anwendung kommen. Außer den bereits genannten halogensubstituierten Phosphaten können beispielsweise auch anorganische oder organische Flammschutzmittel wie roter Phosphor, Aluminiumoxidhydrat, Antimontrioxid, Arsenoxid, Ammoniumpolyphosphat und Calciumsulfat, Blähgraphit oder Cyanursäurederivate wie z.B. Melamin oder Mischungen aus zwei Flammschutzmitteln wie z.B. Ammoniumpolyphosphaten und Melamin sowie gegebenenfalls Maisstärke oder Ammoniumpolyphosphat, Melamin und Blähgraphit und/oder gegebenenfalls aromatische Polyester zum Flammfestmachen der Polyisocyanat-Polyadditionsprodukte verwendet werden. Unter Kettenverlängerern werden bifunktionelle Verbindungen verstanden. Derartige Verbindungen sind dem Fachmann als solche bekannt. Geeignete Kettenverlängerer sind beispielsweise aliphatische, cycloaliphatische und/oder aromatische Diole mit zwei bis vierzehn, vorzugsweise zwei bis zehn Kohlenstoffatomen, wie Ethylenglycol, 1 ,2-Propandiol, 1 ,3-Propandiol, 1 ,2-Pentandiol, 1 ,3-Pentandiol, 1 , 10-Dekandiol, 1 ,2-Dihydroxycyclohexan, 1 ,3-Dihydroxycyclohexan, 1 ,4-Dihydroxycyclohexan, Diethylenglycol, Triethylenglycol, Dipropylenglycol, Tripropylenglycol, 1 ,4-Butandiol, 1 ,6-Hexandiol und Bis-(2-hydroxyethyl)-hydrochinon. In addition, for example, bromine-containing flame retardants can be used. The bromine-containing flame retardants used are preferably compounds which are reactive toward the isocyanate group. Such compounds are, for example, esters of tetrabromophthalic acid with aliphatic diols and alkoxylation products of dibromobutenediol. Compounds derived from the brominated, OH group-containing neopentyl compounds may also be used. In addition to the halogen-substituted phosphates already mentioned, for example, inorganic or organic flame retardants such as red phosphorus, alumina hydrate, antimony trioxide, arsenic oxide, ammonium polyphosphate and calcium sulfate, expandable graphite or cyanuric acid derivatives such as melamine or mixtures of two flame retardants such as ammonium polyphosphates and melamine and optionally corn starch or ammonium polyphosphate, melamine and expandable graphite and / or optionally aromatic polyesters are used to flame-retard the polyisocyanate polyaddition products. Chain extenders are understood to mean bifunctional compounds. Such compounds are known in the art as such. Suitable chain extenders are, for example, aliphatic, cycloaliphatic and / or aromatic diols having two to fourteen, preferably two to ten carbon atoms, such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-pentanediol, 1,3-pentanediol, 1, 10-decanediol, 1,2-dihydroxycyclohexane, 1,3-dihydroxycyclohexane, 1,4-dihydroxycyclohexane, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, 1,6-hexanediol and bis (2-hydroxyethyl ) hydroquinone.
In Schritt I I) wird die in Schritt I) bereitgestellte reaktive Mischung in ein formgebendes Werkzeug injiziert. Verfahren hierzu sind dem Fachmann bekannt. Üblicherweise erfolgt die Injektion der reaktiven Mischung in das formgebende Werkzeug diskontinuierlich. In step I I), the reactive mixture provided in step I) is injected into a forming tool. Processes for this are known to the person skilled in the art. Usually, the injection of the reactive mixture into the forming tool is discontinuous.
Die Injektion der reaktiven Mischung kann beispielsweise unter erhöhtem Druck erfolgen. The injection of the reactive mixture can be carried out, for example, under elevated pressure.
Der Umsatz der reaktiven Mischung, bezogen auf die Isocyanatgruppen, liegt während Schritt I I) bevorzugt bei weniger als 90 %. Die Menge an reaktiver Mischung, die in Schritt I I) in das formgebende Werkzeug injiziert wird, wird so bemessen, dass der in Schritt IV) erhaltene Reaktivschaumstoff die gewünschte Gesamtdichte und Schaumstoffstruktur aufweist. Ist der Reaktivschaumstoff ein Integralschaumstoff, so ist es bevorzugt, dass der Verdichtungsgrad im Bereich von 1 ,05 bis 4, bevorzugt im Bereich von 1 , 1 bis 3, liegt. The conversion of the reactive mixture, based on the isocyanate groups, during step I I) is preferably less than 90%. The amount of reactive mixture injected into the forming tool in step I) is such that the reactive foam obtained in step IV) has the desired overall density and foam structure. If the reactive foam is an integral foam, it is preferred that the degree of compaction is in the range of from 1.05 to 4, preferably in the range of 1.1 to 3.
Als Verdichtungsgrad bezeichnet man das Verhältnis aus der Enddichte des Reaktivschaumstoffs hergestellt durch das Formschäumverfahren zu der Dichte des frei geschäumten Reaktivschaumstoffs. Das formgebende Werkzeug kann Träger- und/oder Trennschichten umfassen. Derartige Träger- und/oder Trennschichten sind dem Fachmann bekannt. Vorzugsweise ist die Träger- und/oder Trennschicht eine Schicht (S2). Für diese Träger- und/oder Trennschicht gelten die weiter unten beschriebenen Ausführungen und Bevorzugungen für die Schicht (S2). In Schritt II I) wird die reaktive Mischung expandiert. Die Expansion der reaktiven Mischung erfolgt durch die Reaktion der ersten Komponente (K1 ) mit der zweiten Komponente (K2). Derartige Reaktionen sind dem Fachmann bekannt. Zudem kann die Expansion gefördert werden durch das gegebenenfalls in der reaktiven Mischung enthaltende chemische und/oder physikalische Treibmittel. The degree of compaction is the ratio of the final density of the reactive foam produced by the foam molding process to the density of the free-foamed reactive foam. The forming tool may comprise carrier and / or release layers. Such carrier and / or separating layers are known to the person skilled in the art. Preferably, the carrier and / or release layer is a layer (S2). The embodiments and preferences for the layer (S2) described below apply to this carrier and / or release layer. In step II I) the reactive mixture is expanded. The expansion of the reactive mixture takes place by the reaction of the first component (K1) with the second component (K2). Such reactions are known in the art. In addition, the expansion may be promoted by the chemical and / or physical blowing agent optionally contained in the reactive mixture.
Die Expansion der reaktiven Mischung kann beispielsweise initiiert werden durch den gegebenenfalls in der reaktiven Mischung enthaltenen Katalysator. The expansion of the reactive mixture may be initiated, for example, by the catalyst optionally contained in the reactive mixture.
Während der Expansion der reaktiven Mischung wird die reaktive Mischung so weit expandiert, dass der erhaltene expandierte Schaumstoff das formgebende Werkzeug vollständig ausfüllt. Enthält das formgebende Werkzeug Träger- und/oder Trennschichten, so verbindet sich der expandierte Schaumstoff mit diesen. During expansion of the reactive mixture, the reactive mixture is expanded to the extent that the resulting expanded foam completely fills the molding tool. Contains the forming tool carrier and / or release layers, so the expanded foam connects to these.
Die Formwerkzeugtemperatur während Schritt I II) liegt üblicherweise im Bereich von 20 bis 200 °C, vorzugsweise im Bereich von 30 bis 140 °C, besonders bevorzugt im Bereich von 30 bis 80 °C. Bevorzugt liegt die Formwerkzeugtemperatur während sämtlichen Schritten I) bis IV) des Formschäumverfahrens im Bereich von 20 bis 200 °C, bevorzugt im Bereich von 30 bis 140 °C, insbesondere bevorzugt im Bereich von 30 bis 80 °C. The mold temperature during step I II) is usually in the range of 20 to 200 ° C, preferably in the range of 30 to 140 ° C, particularly preferably in the range of 30 to 80 ° C. Preferably, the mold temperature during all steps I) to IV) of the foam molding process in the range of 20 to 200 ° C, preferably in the range of 30 to 140 ° C, particularly preferably in the range of 30 to 80 ° C.
In Schritt IV) wird der in Schritt I II) erhaltene expandierte Schaumstoff aus dem formgebenden Werkzeug entformt unter Erhalt des Reaktivschaumstoffs. In step IV), the expanded foam obtained in step I II) is removed from the forming tool to obtain the reactive foam.
Verfahren zur Entformung des in Schritt II I) erhaltenen expandierten Schaumstoff sind dem Fachmann als solche bekannt. Processes for demolding the expanded foam obtained in step II) are known to the person skilled in the art.
Bevorzugt wird das Formschäumverfahren zur Herstellung des Reaktivschaumstoffs als one-shot-Verfahren durchgeführt, besonders bevorzugt mit Hilfe der Niederdruck- Technik oder der Hochdruck-Technik. Dabei werden üblicherweise geschlossene und gegebenenfalls temperierte formgebende Werkzeuge eingesetzt. Das one-shot- Verfahren wird für Polyurethane beispielsweise beschrieben von Piechota und Röhr in "Integralschaumstoff", Carl-Hanser-Verlag, München, Wien, 1975, oder im„Kunststoffhandbuch", Band 7, Polyurethane, 3. Auflage, 1993, Kapitel 7. Ein one-shot-Verfahren ist dem Fachmann als solches bekannt. Beim one-shot-Verfahren werden die Schritte I) und I I) direkt nacheinander oder gleichzeitig durchgeführt. Üblicherweise werden im one-shot-Verfahren die in der reaktiven Mischung enthaltene erste Komponente (K1 ) und die zweite Komponente (K2) sowie gegebenenfalls die weiteren Komponenten, der Katalysator und die weiteren Additive während der Injektion in das formgebende Werkzeug miteinander vermischt, beispielsweise in einem statischen oder dynamischen Mischer. The foam molding process for producing the reactive foam is preferably carried out as a one-shot process, particularly preferably using the low-pressure technique or the high-pressure technique. In this case, usually closed and optionally tempered shaping tools are used. The one-shot process for polyurethanes is described, for example, by Piechota and Röhr in "Integralschaumstoff", Carl Hanser Verlag, Munich, Vienna, 1975, or in the "Kunststoffhandbuch", Volume 7, Polyurethane, 3rd edition, 1993, Chapter 7. A one-shot method is known to those skilled in the art. In the one-shot method, steps I) and II) are carried out directly one after the other or simultaneously. Usually, in the one-shot process, the first component (K1) and the second component (K2) present in the reactive mixture and, if appropriate, the further components, the catalyst and the further additives are mixed with one another during the injection into the shaping tool, for example in US Pat a static or dynamic mixer.
Der erhaltene Reaktivschaumstoff kann in Anschluss an Schritt IV) gegebenenfalls spanend und/oder thermisch bearbeitet werden. Verfahren hierzu sind dem Fachmann als solche bekannt. Vorzugsweise findet nach der Entformung gemäß Schritt IV) keine spanende und/oder thermische Bearbeitung des Reaktivschaumstoffs statt. The resulting reactive foam can be processed optionally after cutting and / or thermally in connection with step IV). Methods for this purpose are known to those skilled in the art. Preferably, after removal from the mold in accordance with step IV), no cutting and / or thermal processing of the reactive foam takes place.
Bezogen auf ein rechtwinkliges Koordinatensystem wird die Länge des so erhaltenen Reaktivschaumstoffs als x-Richtung bezeichnet, die Breite als y-Richtung und die Dicke als z-Richtung. With reference to a rectangular coordinate system, the length of the reactive foam thus obtained is referred to as the x-direction, the width as the y-direction and the thickness as the z-direction.
Der erfindungsgemäße Reaktivschaumstoff kann beliebige Größen aufweisen. The reactive foam of the invention may have any size.
Üblicherweise weist der erfindungsgemäß hergestellte Reaktivschaumstoff eine Dicke (z-Richtung) im Bereich von 4 bis 200 mm, vorzugsweise im Bereich von 5 bis 60 mm, eine Länge (x-Richtung) von mindestens 200 mm, vorzugsweise von mindestens 400 mm und eine Breite (y-Richtung) von mindestens 200 mm, vorzugsweise von mindestens 400 mm auf. Der Reaktivschaumstoff weist üblicherweise eine Länge (x-Richtung) von maximal 4000 mm, bevorzugt von maximal 2500 mm und/oder eine Breite (y-Richtung) von maximal 4000 mm, bevorzugt von maximal 2500 mm auf. Usually, the reactive foam produced according to the invention has a thickness (z-direction) in the range of 4 to 200 mm, preferably in the range of 5 to 60 mm, a length (x-direction) of at least 200 mm, preferably of at least 400 mm and a width (y-direction) of at least 200 mm, preferably of at least 400 mm. The reactive foam usually has a length (x-direction) of not more than 4000 mm, preferably of not more than 2500 mm, and / or a width (y-direction) of not more than 4000 mm, preferably of not more than 2500 mm.
Der Reaktivschaumstoff ist vorzugsweise auf Basis eines Polyurethans, eines Polyharnstoffs oder eines Polyisocyanurats. Insbesondere bevorzugt ist der Reaktivschaumstoff auf Basis eines Polyurethans. The reactive foam is preferably based on a polyurethane, a polyurea or a polyisocyanurate. Particularly preferred is the reactive foam based on a polyurethane.
Ist der Reaktivschaumstoff auf Basis eines Polyurethans, eines Polyharnstoffs oder eines Polyisocyanurats, so bedeutet dies im Rahmen der vorliegenden Erfindung, dass der Reaktivschaumstoff neben dem Polyurethan, dem Polyharnstoff oder dem Polyisocyanurat weitere Polymere enthalten kann, beispielsweise als Blend aus dem Polyurethan, dem Polyharnstoff oder dem Polyisocyanurat und einem weiteren Polymer. Verfahren zur Herstellung dieser Blends sind dem Fachmann bekannt. Ist der Reaktivschaumstoff auf Basis eines Polyurethans, so ist es außerdem bevorzugt, dass es sich um einen Polyurethanschaumstoff, insbesondere um einen Polyurethanhalbhartschaumstoff, um einen Polyurethanweichschaumstoff oder um einen Polyurethanhartschaumstoff handelt. If the reactive foam based on a polyurethane, a polyurea or a polyisocyanurate, it means in the present invention that the reactive foam in addition to the polyurethane, polyurea or polyisocyanurate may contain other polymers, for example as a blend of the polyurethane, the polyurea or the polyisocyanurate and another polymer. Processes for the preparation of these blends are known to the person skilled in the art. If the reactive foam based on a polyurethane, it is also preferred that it is a polyurethane foam, in particular a Semi-rigid polyurethane foam, a flexible polyurethane foam or a polyurethane rigid foam.
Darüber hinaus ist es bevorzugt, dass der Reaktivschaumstoff auf Basis eines Polyurethans, eines Polyharnstoffs oder eines Polyisocyanurats ist, das jeweils nach einem Formschäumverfahren, umfassend die oben genannten Schritte I) bis IV) hergestellt wird, und bei dem die in Schritt I) bereitgestellte reaktive Mischung als erste Komponente (K1 ) mindestens ein Polyisocyanat und als zweite Komponente (K2) mindestens eine Verbindung mit gegenüber Isocyanaten reaktiven Gruppen sowie als weitere Komponente mindestens ein Treibmittel enthält. In addition, it is preferred that the reactive foam is based on a polyurethane, a polyurea or a polyisocyanurate, which is prepared in each case by a foam molding process comprising the abovementioned steps I) to IV), and in which the reactive Mixture as the first component (K1) at least one polyisocyanate and as a second component (K2) at least one compound containing isocyanate-reactive groups and as further component at least one blowing agent.
Am meisten bevorzugt ist der Reaktivschaumstoff auf Basis eines Polyurethans, das nach einem Formschäumverfahren, umfassend die oben genannten Schritte I) bis IV) hergestellt wird und bei dem die erste Komponente (K1 ) ausgewählt ist aus Diphenylmethyldiisocyanat und polymeren Diphenylmethandiisocyanat und die zweite Komponente (K2) mindestens eine Verbindung mit gegenüber Isocyanaten reaktiven Gruppen ist, die ausgewählt ist aus der Gruppe bestehend aus Polyetherpolyolen, Polyesterpolyolen und Polyaminen, wobei die mindestens eine Verbindung mit gegenüber Isocyanaten reaktiven Gruppen eine Funktionalität von 2 bis 8 aufweist und wobei, wenn die zweite Komponente (K2) ausgewählt ist aus Polyetherpolyolen und Polyesterpolyolen, die mindestens eine Verbindung mit gegenüber Isocyanaten reaktiven Gruppen eine mittlere Hydroxylzahl von 12 bis 1200 mg KOH/g aufweist und die reaktive Mischung eine weitere Komponente, die mindestens ein Treibmittel, das Wasser enthält, umfasst. Most preferred is the reactive foam based on a polyurethane prepared by a foam molding process comprising the above-mentioned steps I) to IV) and wherein the first component (K1) is selected from diphenylmethyl diisocyanate and polymeric diphenylmethane diisocyanate and the second component (K2 ) is at least one compound having isocyanate-reactive groups which is selected from the group consisting of polyether polyols, polyester polyols and polyamines, wherein the at least one compound having isocyanate-reactive groups has a functionality of 2 to 8 and wherein when the second component ( K2) is selected from polyether polyols and polyester polyols having at least one compound having isocyanate-reactive groups an average hydroxyl number of 12 to 1200 mg KOH / g and the reactive mixture comprises a further component containing at least one propellant containing water.
Für die in der in Schritt I) bereitgestellten reaktiven Mischung enthaltene erste Komponente (K1 ) und die zweite Komponente (K2) gelten die zuvor beschriebenen Ausführungen und Bevorzugungen für die erste Komponente (K1 ) und die zweite Komponente (K2) entsprechend. For the first component (K1) and the second component (K2) contained in the reactive mixture provided in step I), the previously described embodiments and preferences for the first component (K1) and the second component (K2) apply accordingly.
Der Reaktivschaumstoff weist üblicherweise eine Glasübergangstemperatur von mindestens 80 °C, bevorzugt von mindestens 1 10 °C und insbesondere bevorzugt von mindestens 130 °C auf, bestimmt mittels Differenzthermoanalyse (DTA; differential scanning calorimetry; DSC). Die Glasübergangstemperatur des Reaktivschaumstoffs liegt im Allgemeinen bei höchstens 400 °C, bevorzugt bei höchstens 300 °C, insbesondere bei höchstens 200 °C, bestimmt mittels Differenzthermoanalyse (DTA). The reactive foam usually has a glass transition temperature of at least 80 ° C., preferably of at least 110 ° C. and more preferably of at least 130 ° C., determined by differential scanning calorimetry (DTA). The glass transition temperature of the reactive foam is generally not more than 400 ° C., preferably not more than 300 ° C., in particular not more than 200 ° C., determined by means of differential thermal analysis (DTA).
Gegenstand der vorliegenden Erfindung ist außerdem ein Paneel, das mindestens einen erfindungsgemäßen Formkörper und mindestens eine Schicht (S1 ) umfasst. Ein „Paneel" kann gegebenenfalls in Fachkreisen auch als „Sandwich", „Sandwichmaterial",„Laminat" und/oder„Compositartikel" bezeichnet werden. In einer bevorzugten Ausführungsform des Paneels weist das Paneel zwei Schichten (S1 ) auf, und die beiden Schichten (S1 ) sind jeweils an einer Seite des Formkörpers angebracht, die der jeweils anderen Seite im Formkörper gegenüberliegt. The subject of the present invention is also a panel comprising at least one shaped body according to the invention and at least one layer (S1). A "panel" may also be referred to in the art as "sandwich", "sandwich material", "laminate" and / or "composite article". In a preferred embodiment of the panel, the panel has two layers (S1), and the two layers (S1) are each attached to one side of the shaped body opposite to the other side in the molded body.
In einer Ausführungsform des erfindungsgemäßen Paneels umfasst die Schicht (S1 ) mindestens ein Harz, vorzugsweise ist das Harz ein reaktives duroplastisches oder thermoplastisches Harz, mehr bevorzugt ist das Harz auf der Basis von Epoxiden, Acrylaten, Polyurethanen, Polyamiden, Polyestern, ungesättigten Polyestern, Vinylestern oder Mischungen daraus, insbesondere ist das Harz ein aminisch härtendes Epoxidharz, ein latent härtendes Epoxidharz, ein anhydridisch härtendes Epoxidharz oder ein Polyurethan aus Isocyanaten und Polyolen. Derartige Harzsysteme sind dem Fachmann bekannt, beispielsweise aus Penczek et al. (Advances in Polymer Science, 184, S. 1 - 95, 2005), Pham et al. (Ullmann's Encyclopedia of Industrial Chemistry, Vol. 13, 2012), Fahnler (Polyamide, Kunststoff Handbuch 3/4, 1998) und Younes (W012134878 A2). In one embodiment of the panel according to the invention, the layer (S1) comprises at least one resin, preferably the resin is a reactive thermosetting or thermoplastic resin, more preferably the resin is based on epoxides, acrylates, polyurethanes, polyamides, polyesters, unsaturated polyesters, vinyl esters or mixtures thereof, in particular the resin is an amine-curing epoxy resin, a latent curing epoxy resin, an anhydride-curing epoxy resin or a polyurethane of isocyanates and polyols. Such resin systems are known to the person skilled in the art, for example from Penczek et al. (Advances in Polymer Science, 184, pp. 1-95, 2005), Pham et al. (Ullmann's Encyclopedia of Industrial Chemistry, Vol. 13, 2012), Fahnler (Polyamides, Plastics Handbook 3/4, 1998) and Younes (W012134878 A2).
Erfindungsgemäß bevorzugt ist außerdem ein Paneel, bei dem i) der Faserbereich (FB1 ) der Faser (F) teilweise oder vollständig, vorzugsweise vollständig, mit der ersten Schicht (S1 ) in Kontakt ist, und/oder ii) der Faserbereich (FB3) der Faser (F) teilweise oder vollständig, vorzugsweise vollständig, mit der zweiten Schicht (S1 ) in Kontakt ist, und/oder iii) das Paneel zwischen mindestens einer Seite des Formkörpers und mindestens einer Schicht (S1 ) mindestens eine Schicht (S2) aufweist, vorzugsweise ist die Schicht (S2) aus flächigen Fasermaterialien oder polymeren Folien, mehr bevorzugt aus porösen flächigen Fasermaterialien oder porösen polymeren Folien, insbesondere bevorzugt aus Papier, Glasfasern oder Kohlenstofffasern inAlso preferred according to the invention is a panel in which i) the fiber region (FB1) of the fiber (F) is partially or completely, preferably completely, in contact with the first layer (S1), and / or ii) the fiber region (FB3) Fiber (F) is partially or completely, preferably completely, in contact with the second layer (S1), and / or iii) the panel has at least one layer (S2) between at least one side of the shaped body and at least one layer (S1), Preferably, the layer (S2) of sheet-like fiber materials or polymeric films, more preferably of porous sheet-like fiber materials or porous polymeric films, particularly preferably of paper, glass fibers or carbon fibers in
Form von Vliesen, Gelegen oder Geweben. Form of nonwovens, layers or fabrics.
Als Porosität wird das Verhältnis (dimensionslos) von Hohlraumvolumen (Porenvolumen) zu dem Gesamtvolumen eines Reaktivschaumstoffs bezeichnet. Sie wird beispielsweise durch bildanalytische Auswertung mikroskopischer Aufnahmen bestimmt, indem das Hohlraum- bzw. Porenvolumen durch das Gesamtvolumen geteilt wird. Die Gesamtporosität eines Stoffes setzt sich zusammen aus der Summe der Hohlräume, die untereinander und mit der Umgebung in Verbindung stehen (offene Porosität) und den nicht miteinander verbundenen Hohlräumen (geschlossene Porosität). Bevorzugt sind Schichten (S2), die eine hohe offene Porosität aufweisen. In einer weiteren erfindungsgemäßen Ausführungsform des Paneels enthält die mindestens eine Schicht (S1 ) zusätzlich mindestens ein faserförmiges Material, wobei i) das faserförmige Material Fasern in Form von einer oder mehreren Lagen aus Schnittfasern, Vliesen, Gelegen, Gestricken und/oder Geweben, bevorzugt inPorosity is the ratio (dimensionless) of void volume (pore volume) to the total volume of a reactive foam. It is determined for example by image analysis of microscopic images by the void or pore volume is divided by the total volume. The total porosity of a substance is made up of the sum of the voids that communicate with each other and the environment (open porosity) and the non-interconnected voids (closed porosity). Preference is given to layers (S2) which have a high open porosity. In a further embodiment of the panel according to the invention, the at least one layer (S1) additionally comprises at least one fibrous material, i) the fibrous material comprising fibers in the form of one or more layers of cut fibers, nonwovens, loops, knits and / or fabrics, preferably in
Form von Gelegen oder Geweben, besonders bevorzugt in Form von Gelegen oder Geweben mit einem Flächengewicht pro Gelege bzw. Gewebe von 150 bis 2500 g/m2 enthält, und/oder ii) das faserförmige Material Fasern aus organischen, anorganischen, metallischen oder keramischen Fasern, bevorzugt polymere Fasern, Basaltfasern, Glasfasern, Kohlenstofffasern oder Naturfasern, besonders bevorzugt Glasfasern oder Kohlenstofffasern enthält. Für die Naturfasern und die polymeren Fasern gelten die zuvor beschriebenen Ausführungen. Form of loops or fabrics, more preferably in the form of loops or fabrics having a basis weight per fabric of from 150 to 2500 g / m 2 , and / or ii) the fibrous material comprises fibers of organic, inorganic, metallic or ceramic fibers , preferably polymeric fibers, basalt fibers, glass fibers, carbon fibers or natural fibers, particularly preferably glass fibers or carbon fibers. For the natural fibers and the polymeric fibers apply the previously described embodiments.
Eine Schicht (S1 ), die zusätzlich mindestens ein faserförmiges Material enthält, wird auch als faserverstärkte Schicht, insbesondere als faserverstärkte Harzschicht, sofern die Schicht (S1 ) ein Harz umfasst, bezeichnet. A layer (S1) which additionally contains at least one fibrous material is also referred to as a fiber-reinforced layer, in particular as a fiber-reinforced resin layer, if the layer (S1) comprises a resin.
Figur 2 zeigt eine weitere bevorzugte Ausführungsform der vorliegenden Erfindung. In einer zweidimensionalen Seitansicht ist ein erfindungsgemäßes Paneel (7) dargestellt, das einen erfindungsgemäßen Formkörper (1 ) umfasst, wie beispielsweise vorstehend im Rahmen der Ausführungsform zu Figur 1 dargestellt. Soweit nicht anders ausgeführt, haben die Bezugszeichen bei sonstigen Abkürzungen in den Figuren 1 und 2 die gleiche Bedeutung. Figure 2 shows another preferred embodiment of the present invention. In a two-dimensional side view, an inventive panel (7) is shown, which comprises a molded body (1) according to the invention, as shown for example in the context of the embodiment of FIG. Unless otherwise stated, the reference numerals in other abbreviations in Figures 1 and 2 have the same meaning.
Bei der Ausführungsform gemäß Figur 2 umfasst das erfindungsgemäße Paneel zwei Schichten (S1 ), die durch (5) und (6) dargestellt sind. Die beiden Schichten (5) und (6) befinden sich somit an jeweils zu einander gegenüberliegenden Seiten des Formkörpers (1 ). Bei den beiden Schichten (5) und (6) handelt es sich vorzugsweise um Harzschichten oder faserverstärkte Harzschichten. Wie aus Figur 2 weiterhin ersichtlich, sind die beiden Enden der Faser (4) von der jeweiligen Schicht (5) bzw. (6) umschlossen. In the embodiment according to FIG. 2, the panel according to the invention comprises two layers (S1), which are represented by (5) and (6). The two layers (5) and (6) are thus located on mutually opposite sides of the shaped body (1). The two layers (5) and (6) are preferably resin layers or fiber-reinforced resin layers. As can also be seen from FIG. 2, the two ends of the fiber (4) are enclosed by the respective layer (5) or (6).
Gegebenenfalls können zwischen dem Formkörper (1 ) und der ersten Schicht (5) und/oder zwischen dem Formkörper (1 ) und der zweiten Schicht (6) eine oder mehrere weitere Schichten enthalten sein. Wie vorstehend für Figur 1 beschrieben, ist auch in Figur 2 der Einfachheit halber eine einzige Faser (F) durch (4) dargestellt. Hinsichtlich der Anzahl an Fasern bzw. Faserbündeln in der Praxis gelten die sinngemäßen Aussagen wie vorstehend für Figur 1 aufgeführt. If appropriate, one or more further layers may be present between the shaped body (1) and the first layer (5) and / or between the shaped body (1) and the second layer (6). As described above for FIG. 1, also in FIG. 2, for the sake of simplicity, a single fiber (F) is represented by (4). Regarding the number of fibers or fiber bundles in practice apply the analogous statements as listed above for Figure 1.
Darüber hinaus ist ein Paneel bevorzugt, bei dem zumindest eine der folgenden Alternativen erfüllt ist: i) der im Paneel enthaltene Formkörper enthält mindestens eine Seite, die nicht mechanisch und/oder thermisch bearbeitet wurde, und/oder ii) der im Paneel enthaltene Formkörper weist mindestens eine Schicht (S2) auf, die im Formschäumverfahren umfassend die Schritte I) bis V), in Schritt I I) als Trägerfolie auf den Reaktivschaumstoff aufgebracht wurde, und/oder iii) die mindestens eine Schicht (S1 ) umfasst ein Harz und der Reaktivschaumstoff des Formkörpers weist eine Harzaufnahme von weniger als 1000 g/m2, bevorzugt von weniger als 500 g/m2 und besonders bevorzugt von weniger als 100 g/m2 auf, und/oder iv) das Paneel weist eine Schälfestigkeit von mehr als 200 J/m2, bevorzugt von mehr als 500 J/m2, besonders bevorzugt von mehr als 2000 J/m2 auf, und/oder v) der Reaktivschaumstoff des im Paneel enthaltenen Formkörpers weist eine spezifische Scherfestigkeit, gemessen parallel zu der mindestens einen Schicht (S1 ), im Bereich von 2 bis 25 kPa/(kg/m3), bevorzugt im Bereich von 3 bis 15 kPa/(kg/m3), besonders bevorzugt im Bereich von 4 bis 12 kPa/(kg/m3) auf, und/oder vi) der Reaktivschaumstoff des im Paneel enthaltenen Formkörpers weist ein Schubmodul gemessen parallel zu der mindestens einen Schicht (S1 ) im Bereich von 0,05 bis 0,6 MPa/(kg/m3), bevorzugt im Bereich von 0,05 bis 0,5In addition, a panel is preferred in which at least one of the following alternatives is fulfilled: i) the molded body contained in the panel contains at least one side which has not been mechanically and / or thermally processed, and / or ii) comprises the molded body contained in the panel at least one layer (S2) which was applied as a carrier film to the reactive foam in the foam-forming process comprising steps I) to V) in step II), and / or iii) the at least one layer (S1) comprises a resin and the reactive foam of the shaped body has a resin absorption of less than 1000 g / m 2 , preferably less than 500 g / m 2 and particularly preferably less than 100 g / m 2 , and / or iv) the panel has a peel strength of more than 200 J / m 2 , preferably of more than 500 J / m 2 , more preferably of more than 2000 J / m 2 , and / or v) the reactive foam of the molding contained in the panel has a specific shear strength, measured in parallel to the at least one layer (S1), in the range of 2 to 25 kPa / (kg / m 3 ), preferably in the range of 3 to 15 kPa / (kg / m 3 ), particularly preferably in the range of 4 to 12 kPa / (kg / m 3 ) on, and / or vi) the reactive foam of the molding contained in the panel has a shear modulus measured parallel to the at least one layer (S1) in the range of 0.05 to 0.6 MPa / (kg / m 3 ), preferably in the range of 0.05 to 0.5
MPa/(kg/m3), besonders bevorzugt im Bereich von 0,05 bis 0,2 MPa/(kg/m3) auf, und/oder vii) der im Paneel enthaltene Formkörper weist eine spezifische Scherfestigkeit gemessen parallel zu der mindestens einen Schicht (S1 ) von mindestensMPa / (kg / m 3 ), more preferably in the range of 0.05 to 0.2 MPa / (kg / m 3 ) on, and / or vii) the molded body contained in the panel has a specific shear strength measured in parallel to the at least a layer (S1) of at least
5 kPa/(kg/m3), bevorzugt von mindestens 8 kPa/(kg/m3), besonders bevorzugt von mindestens 12 kPa/(kg/m3) auf, und/oder viii) der im Paneel enthaltene Formkörper weist im Paneel ein Schubmodul gemessen parallel zu der mindestens einen Schicht (S1 ) von mindestens 0,2 MPa/(kg/m3), bevorzugt von mindestens 0,6 MPa/(kg/m3), besonders bevorzugt von mindestens 1 ,0 MPa/(kg/m3), auf. 5 kPa / (kg / m 3 ), preferably of at least 8 kPa / (kg / m 3 ), particularly preferably of at least 12 kPa / (kg / m 3 ), and / or viii) the molding contained in the panel has in Panel a shear modulus measured parallel to the at least one layer (S1) of at least 0.2 MPa / (kg / m 3 ), preferably of at least 0.6 MPa / (kg / m 3 ), more preferably of at least 1, 0 MPa / (kg / m 3 ), on.
Die spezifische Scherfestigkeit und das Schubmodul werden gemäß DI N 53294 (Stand: 1982) und die Dichte nach ISO 845 (Stand: 2007) bestimmt. The specific shear strength and the shear modulus are determined according to DI N 53294 (as of 1982) and the density according to ISO 845 (as of 2007).
Das Schubmodul des Formkörpers gemäß Alternative vi) bezieht sich auf das Schubmodul des Formkörpers ohne die mindestens eine Schicht (S1 ). Lediglich die Messung erfolgt parallel zu der Seite, an der im Paneel die mindestens eine Schicht (S1 ) aufgebracht wird. The shear modulus of the molding according to alternative vi) refers to the shear modulus of the molding without the at least one layer (S1). Only the measurement takes place parallel to the side at which the at least one layer (S1) is applied in the panel.
Die Schälfestigkeit des Paneels wird mit Single cantilever beam (SCB)-Proben bestimmt. Die Dicke der Formkörper liegt bei 20 mm, die Schichten (S1 ) bestehen aus jeweils etwa 2 mm dicken quasiisotropen glasfaserverstärkten Epoxidharzschichten. Die Paneele werden dann in einer Zwick Z050 Zugprüfmaschine mit einer Geschwindigkeit von 5 mm/min geprüft, wobei das Paneel drei- bis viermal be- und entlastet wird. Das Risswachstum bzw. der Zuwachs bei jedem Belastungszyklus (Aa) wird optisch ermittelt. Aus dem Kraft-Weg-Verlauf wird die Risswachstumsenergie (AU) ermittelt. Daraus wird die Risszähigkeit bzw. Schälfestigkeit ermittelt als The peel strength of the panel is determined with single cantilever beam (SCB) samples. The thickness of the moldings is 20 mm, the layers (S1) each consist of about 2 mm thick quasi-isotropic glass fiber reinforced epoxy resin. The panels are then tested in a Zwick Z050 tensile testing machine at a speed of 5 mm / min, loading and unloading the panel three to four times. The crack growth or the increase in each load cycle (Aa) is determined optically. The crack growth energy (AU) is determined from the force-displacement curve. From this, the fracture toughness or peel strength is determined as
mit B als Probenbreite. with B as sample width.
Zur Bestimmung der Harzaufnahme werden neben den eingesetzten Harzsystemen, dem Reaktivschaumstoff und Glasgelegen die folgende Hilfsmaterialien verwendet: Nylon Vakuumfolie, Vakuumdichtband, Nylon Fließhilfe, Polyolefin Trennfolie, Polyester Abreißgewebe sowie PTFE Membranfolie und Polyester Absaugvlies. Paneele, nachfolgend auch als Sandwichmaterialien bezeichnet, werden aus den Formkörpern durch Aufbringung faserverstärkter Decklagen mittels Vakuuminfusion hergestellt. An der Ober- und Unterseite der (faserverstärkten) Schaumstoffe werden je zwei Lagen Quadrax-Glasgelege (Roving: E-Glass SE1500, OCV; Textil: Saertex, isotropes Laminat [0 -45 90°45°] mit je 1200 g/m2) aufgebracht. Für die Bestimmung der Harzaufnahme wird zwischen dem Formkörper, nachfolgend auch als Kernmaterial bezeichnet, und dem Glasgelege, im Gegensatz zur standardmäßigen Herstellung der Paneele, eine Trennfolie eingelegt. Damit ist die Harzaufnahme des reinen Formkörpers bestimmbar. Auf den Glasgelegen werden beidseitig das Abreißgewebe und die Fließhilfen angebracht. Der Aufbau wird anschließend mit Angüssen für das Harzsystem und Anschlüssen für die Evakuierung ausgestattet. Schließlich wird eine Vakuumfolie über den gesamten Aufbau aufgebracht, mit Dichtband abgedichtet und der gesamte Aufbau evakuiert. Der Aufbau wird auf einem elektrisch beheizbaren Tisch mit einer Glasoberfläche vorbereitet. To determine the resin uptake, the following auxiliary materials are used in addition to the resin systems used, the reactive foam and glass gels: nylon vacuum film, vacuum sealing tape, nylon flow aid, polyolefin release film, polyester tear off fabric and PTFE membrane film and polyester absorbent nonwoven. Panels, also referred to below as sandwich materials, are produced from the moldings by applying fiber-reinforced cover layers by means of vacuum infusion. At the top and bottom of the (fiber-reinforced) foams are each two layers of Quadrax Glasgelege (Roving: E-Glass SE1500, OCV, textile: Saertex, isotropic laminate [0 -45 90 ° 45 °], each 1200 g / m 2 ) applied. For the determination of the resin absorption, a release film is inserted between the molded body, hereinafter also referred to as core material, and the glass scrim, in contrast to the standard production of the panels. Thus, the resin absorption of the pure molded body can be determined. On the glass shelves the tear-off fabric and the flow aids are attached on both sides. The assembly is then fitted with sprues for the resin system and ports for evacuation. Finally, a vacuum film is applied over the entire structure, sealed with sealing tape and evacuated the entire structure. The structure is prepared on an electrically heated table with a glass surface.
Als Harzsystem wird aminisch härtendes Epoxid verwendet (Harz: BASF Baxxores 5 5400, Härter: BASF Baxxodur 5440, Mischungsverhältnis und weitere Verarbeitung nach Datenblatt). Nach dem Mischen der beiden Komponenten wird das Harz für 10 min bei bis zu 20 mbar evakuiert. Bei einer Harztemperatur von 23 +/- 2 °C erfolgt die Infusion auf den vortemperierten Aufbau (Tischtemperatur: 35 °C). Durch anschließende Temperaturrampe von 0,3 K/min von 35 °C auf 75 °C und isothermer0 Aushärtung bei 75 °C für 6 h können Paneele hergestellt werden, die aus den Reaktivschaumstoffen und glasfaserverstärkten Decklagen bestehen. The resin system used is amine-curing epoxy (resin: BASF Baxxores 5 5400, hardener: BASF Baxxodur 5440, mixing ratio and further processing according to data sheet). After mixing the two components, the resin is evacuated for 10 minutes at up to 20 mbar. At a resin temperature of 23 + / - 2 ° C, infusion takes place on the pre-tempered structure (table temperature: 35 ° C). By subsequent temperature ramp of 0.3 K / min from 35 ° C to 75 ° C and isothermal0 curing at 75 ° C for 6 h panels can be made, which consist of the reactive foams and glass fiber reinforced cover layers.
Zu Beginn werden die Formkörper nach ISO 845 (Stand Oktober 2009) vermessen, um die Rohdichte des Formkörpers zu erhalten. Nach dem Aushärten des Harzsystems5 werden die verarbeiteten Paneele besäumt, um überschüssige Harzansammlungen in den Randbereichen durch nicht passend anliegende Vakuumfolie zu eliminieren. At the beginning, the moldings are measured according to ISO 845 (as of October 2009) in order to obtain the density of the molded body. After curing of the resin system 5, the processed panels are trimmed to eliminate excess resin build-up in the peripheral areas by non-conforming vacuum foil.
Anschließend werden die Decklagen entfernt und die enthaltenen Formkörper erneut durch ISO 845 vermessen. Aus der Differenz der Dichten ergibt sich die absolute0 Harzaufnahme. Durch Multiplikation mit der Dicke des Formkörpers ergibt sich die entsprechende Harzaufnahme in kg/m2. Subsequently, the cover layers are removed and the moldings contained are measured again by ISO 845. The difference between the densities results in the absolute resin absorption. By multiplying by the thickness of the shaped body, the corresponding resin absorption results in kg / m 2 .
Gegenstand der vorliegenden Erfindung ist weiterhin ein Verfahren zur Herstellung des erfindungsgemäßen Formkörpers, wobei mindestens eine Faser (F) in den5 Reaktivschaumstoff teilweise eingebracht wird, wodurch sich die Faser (F) mit dem Faserbereich (FB2) innerhalb des Formkörpers befindet und von dem Reaktivschaumstoff umschlossen ist, während der Faserbereich (FB1 ) der Faser (F) aus einer ersten Seite des Formkörpers herausragt und der Faserbereich (FB3) der Faser (F) aus einer zweiten Seite des Formkörpers herausragt.The present invention furthermore relates to a process for producing the shaped body according to the invention, wherein at least one fiber (F) is partially introduced into the reactive foam, whereby the fiber (F) with the fiber region (FB2) is located inside the shaped body and enclosed by the reactive foam is, while the fiber region (FB1) of the fiber (F) protrudes from a first side of the shaped body and the fiber region (FB3) of the fiber (F) protrudes from a second side of the shaped body.
0 0
Zum Einbringen der Faser (F) und/oder eines Faserbündels eignen sich prinzipiell alle dem Fachmann bekannten Methoden. Geeignete Verfahren sind beispielsweise in WO 2006/125561 oder in WO 201 1/012587 beschrieben. 5 In einer Ausführungsform des erfindungsgemäßen Verfahrens erfolgt das teilweise Einbringen der mindestens einen Faser (F) in den Reaktivschaumstoff durch Einnähen unter Verwendung einer Nadel, vorzugsweise erfolgt das teilweise Einbringen durch die Schritte a) bis f): 0 a) gegebenenfalls Aufbringen von mindestens einer Schicht (S2) auf mindestens eine Seite des Reaktivschaumstoffs, b) Erzeugung von einem Loch je Faser (F) im Reaktivschaumstoff und gegebenenfalls in der Schicht (S2), wobei sich das Loch von einer ersten Seite zu einer zweiten Seite des Reaktivschaumstoffs und gegebenenfalls durch die Schicht (S2) erstreckt, c) Bereitstellung von mindestens einer Faser (F) auf der zweiten Seite des Reaktivschaumstoffs, d) Durchführen einer Nadel von der ersten Seite des Reaktivschaumstoffs durch das Loch zu der zweiten Seite des Reaktivschaumstoffs und gegebenenfalls Durchführung der Nadel durch die Schicht (S2), e) Befestigen von mindestens einer Faser (F) an der Nadel auf der zweiten Seite des Reaktivschaumstoffs, und f) Rückführen der Nadel samt Faser (F) durch das Loch, so dass die Faser (F) sich mit dem Faserbereich (FB2) innerhalb des Formkörpers befindet und von dem Reaktivschaumstoff umschlossen ist, während der Faserbereich (FB1 ) der Faser (F) aus einer ersten Seite des Formkörpers oder gegebenenfalls derIn principle, all methods known to the person skilled in the art are suitable for introducing the fiber (F) and / or a fiber bundle. Suitable processes are described, for example, in WO 2006/125561 or in WO 201 1/012587. In one embodiment of the method according to the invention the partial introduction of the at least one fiber (F) into the reactive foam by sewing using a needle, preferably the partial introduction of steps a) to f): 0 a) optionally applying at least one Layer (S2) on at least one side of the reactive foam, b) producing one hole per fiber (F) in the reactive foam and optionally in the layer (S2), the hole extending from a first side to a second side of the reactive foam and optionally through the layer (S2), c) providing at least one fiber (F) on the second side of the reactive foam, d) passing a needle from the first side of the reactive foam through the hole to the second side of the reactive foam and optionally passing the needle through the layer (S2), e) affixing at least a fiber (F) on the needle on the second side of the reactive foam; and f) returning the needle and fiber (F) through the hole such that the fiber (F) is within the molding with the fiber region (FB2) and of the reactive foam is enclosed, while the fiber region (FB1) of the fiber (F) from a first side of the shaped body or possibly the
Schicht (S2) herausragt und der Faserbereich (FB3) der Faser (F) aus einer zweiten Seite des Formkörpers herausragt, besonders bevorzugt werden die Schritte b) und d) gleichzeitig durchgeführt. Layer (S2) protrudes and the fiber region (FB3) of the fiber (F) protrudes from a second side of the molding, more preferably, the steps b) and d) are carried out simultaneously.
Das Aufbringen von mindestens einer Schicht (S2) in Schritt a) kann beispielsweise wie vorstehend beschrieben während Schritt II) des Formschäumverfahrens erfolgen. The application of at least one layer (S2) in step a) can be carried out, for example, as described above during step II) of the foam molding process.
In einer besonders bevorzugten Ausführungsform werden die Schritte b) und d) gleichzeitig durchgeführt. In dieser Ausführungsform wird das Loch von der ersten Seite zu der zweiten Seite des Reaktivschaumstoffs durch das Durchführen einer Nadel von der ersten Seite des Reaktivschaumstoffs zu der zweiten Seite des Reaktivschaumstoffs erzeugt. In dieser Ausführungsform kann das Einbringen der mindestens einen Faser (F) beispielsweise die folgenden Schritte umfassen: a) gegebenenfalls Aufbringen einer Schicht (S2) auf mindestens eine Seite des Reaktivschaumstoffs, b) Bereitstellen von mindestens einer Faser (F) auf der zweiten Seite des Reaktivschaumstoffs, c) Erzeugung von einem Loch je Faser (F) im Reaktivschaumstoff und gegebenenfalls in der Schicht (S2), wobei sich das Loch von der ersten Seite zu einer zweiten Seite des Reaktivschaumstoffs und gegebenenfalls durch die Schicht (S2) erstreckt und wobei die Erzeugung des Lochs durch das Durchführen einer Nadel durch den Reaktivschaumstoffs und gegebenenfalls durch die Schicht (S2) erfolgt, d) Befestigen von mindestens einer Faser (F) an der Nadel auf der zweiten Seite des Reaktivschaumstoffs, e) Rückführen der Nadel samt Faser (F) durch das Loch, so dass die Faser (F) sich mit dem Faserbereich (FB2) innerhalb des Formkörpers befindet und von demIn a particularly preferred embodiment, steps b) and d) are carried out simultaneously. In this embodiment, the hole is created from the first side to the second side of the reactive foam by passing a needle from the first side of the reactive foam to the second side of the reactive foam. In this embodiment, the introduction of the at least one fiber (F) may comprise, for example, the following steps: a) optionally applying a layer (S2) to at least one side of the reactive foam, b) providing at least one fiber (F) on the second side of the reactive foam; c) producing one hole per fiber (F) in the reactive foam and optionally in the layer (S2), the hole being from the first side to a second one Side of the reactive foam and optionally through the layer (S2) and wherein the hole is created by passing a needle through the reactive foam and optionally through the layer (S2), d) attaching at least one fiber (F) to the needle e) recycling the needle and fiber (F) through the hole so that the fiber (F) is in the body portion with the fiber portion (FB2) and of the second side of the reactive foam
Reaktivschaumstoff umschlossen ist, während der Faserbereich (FB1 ) der Faser (F) aus einer ersten Seite des Formkörpers oder gegebenenfalls aus der Schicht (S2) herausragt und der Faserbereich (FB3) aus einer zweiten Seite des Formkörpers herausragt, f) gegebenenfalls Abschneiden der Faser (F) an der zweiten Seite und g) gegebenenfalls Aufschneiden der an der Nadel gebildeten Schlaufe der Faser (F). Reactive foam is enclosed, while the fiber region (FB1) of the fiber (F) protrudes from a first side of the shaped body or optionally from the layer (S2) and the fiber region (FB3) protrudes from a second side of the shaped body, f) optionally cutting off the fiber (F) on the second side and g) optionally cutting open the loop of the fiber (F) formed on the needle.
In einer bevorzugten Ausführungsform wird als Nadel eine Hakennadel eingesetzt und mindestens eine Faser (F) in Schritt d) in die Hakennadel eingehängt. In a preferred embodiment, a hook needle is used as the needle and at least one fiber (F) hooked into the hook needle in step d).
In einer weiteren bevorzugten Ausführungsform werden mehrere Fasern (F) gleichzeitig in den Reaktivschaumstoff gemäß der vorher beschriebenen Schritte eingebracht. In a further preferred embodiment, a plurality of fibers (F) are simultaneously introduced into the reactive foam according to the previously described steps.
Im erfindungsgemäßen Verfahren ist es außerdem bevorzugt, dass Vertiefungen im Formkörper teilweise oder vollständig vor dem Einbringen von mindestens einer Faser (F) in den Reaktivschaumstoff eingebracht werden. In the method according to the invention, it is also preferred that depressions in the shaped body are introduced partially or completely into the reactive foam before the introduction of at least one fiber (F).
Weiterhin Gegenstand der vorliegenden Erfindung ist ein Verfahren zur Herstellung des erfindungsgemäßen Paneels, bei dem die mindestens eine Schicht (S1 ) als reaktives viskoses Harz auf einen erfindungsgemäßen Formkörper erzeugt, aufgebracht und ausgehärtet wird, vorzugsweise durch Flüssigimprägnierverfahren, besonders bevorzugt durch Druck- bzw. vakuumunterstützte Imprägnierverfahren, insbesondere bevorzugt durch Vakuuminfusion oder druckunterstützte Injektionsverfahren, am meisten bevorzugt durch Vakuuminfusion. Flüssigimprägnierverfahren sind dem Fachmann als solche bekannt und werden beispielsweise in Wiley Encyclopedia of Composites (2nd Edition, Wiley, 2012), Parnas et al. (Liquid Composite Moulding, Hanser, 2000) und Williams et al. (Composites Part A, 27, S. 517 - 524, 1997) ausführlich beschrieben. The present invention further provides a process for the production of the panel according to the invention, in which the at least one layer (S1) is produced, applied and cured as reactive viscous resin on a molded body according to the invention, preferably by liquid impregnation, more preferably by pressure or vacuum assisted impregnation, especially preferably by vacuum infusion or pressure assisted injection methods, most preferably by vacuum infusion. Liquid impregnation methods are known to the person skilled in the art and are described, for example, in Wiley Encyclopedia of Composites (2nd Edition, Wiley, 2012), Parnas et al. (Liquid Composite Molding, Hanser, 2000) and Williams et al. (Composites Part A, 27, pp. 517-524, 1997).
Zur Herstellung des erfindungsgemäßen Paneels können verschiedene Hilfsmaterialien eingesetzt werden. Geeignete Hilfsmaterialien für die Herstellung durch Vakuuminfusion sind beispielsweise Vakuumfolie, bevorzugt aus Nylon, Vakuumdichtband, Fließhilfe, bevorzugt aus Nylon, Trennfolie, bevorzugt aus Polyolefin, Abreißgewebe, bevorzugt aus Polyester sowie eine semipermeable Folie, vorzugsweise eine Membranfolie, besonders bevorzugt eine PTFE Membranfolie und Absaugvlies, bevorzugt aus Polyester. Die Wahl geeigneter Hilfsmaterialien richtet sich nach dem zu fertigenden Bauteil, dem gewählten Prozess und den eingesetzten Materialien, speziell dem Harzsystem. Beim Einsatz von Harzsystemen auf der Basis von Epoxid und Polyurethan werden bevorzugt Fließhilfen aus Nylon, Trennfolien aus Polyolefin, Abreißgewebe aus Polyester sowie eine semipermeable Folien als PTFE- Membranfolien und Absaugvliese aus Polyester eingesetzt. Various auxiliary materials can be used to produce the panel according to the invention. Suitable auxiliary materials for production by vacuum infusion are, for example, vacuum film, preferably nylon, vacuum sealing tape, flow aid, preferably nylon, release film, preferably polyolefin, tear-off fabric, preferably polyester and a semipermeable film, preferably a membrane film, more preferably a PTFE membrane film and Absaugvlies , preferably of polyester. The choice of suitable auxiliary materials depends on the component to be manufactured, the selected process and the materials used, especially the resin system. When using resin systems based on epoxy and polyurethane, preference is given to using nylon flow aids, polyolefin release liners, polyester tear-off fabrics and semipermeable films as PTFE membrane sheets and polyester absorbent sheets.
Diese Hilfsmaterialien können auf verschiedene Arten bei den Verfahren zur Herstellung des erfindungsgemäßen Paneels eingesetzt werden. Paneele werden besonders bevorzugt aus den Formkörpern durch Aufbringung faserverstärkter Decklagen mittels Vakuuminfusion hergestellt. In einem typischen Aufbau werden zur Herstellung des erfindungsgemäßen Paneels an der Ober- und Unterseite der Formkörper faserförmige Materialien und ggf. weitere Schichten aufgebracht. Anschließend werden Abreißgewebe und Trennfolien platziert. Bei der Infusion des flüssigen Harzsystems kann mit Fließhilfen und / oder Membranfolien gearbeitet werden. Besonders bevorzugt sind die folgenden Varianten: i) Einsatz einer Fließhilfe auf nur einer Seite des Aufbaus, und/oder ii) Einsatz einer Fließhilfe auf beiden Seiten des Aufbaus, und/oder iii) Aufbau mit einer semipermeablen Membran (VAP-Aufbau), diese wird vorzugsweise flächig über den Formkörper drapiert, auf dem Fließhilfen, Trennfolie und Abreißgewebe auf einer oder beiden Seiten eingesetzt werden und die semipermeable Membran durch Vakuumdichtband zur Formoberfläche hin abgedichtet wird, das Absaugvlies wird auf der Formkörper fremden Seite der semipermeablen Membran eingesetzt wodurch die Luft flächig nach oben evakuiert wird, und/oder iv) Verwendung einer Vakuumtasche aus Membranfolie, die bevorzugt auf die gegenüberliegende Anguss-Seite des Formkörpers platziert wird, womit die Luft von der gegenüberliegenden Seite zum Anguss evakuiert wird. These auxiliary materials can be used in various ways in the processes for producing the panel according to the invention. Panels are particularly preferably produced from the moldings by applying fiber-reinforced cover layers by means of vacuum infusion. In a typical structure, fibrous materials and optionally further layers are applied to the upper and lower sides of the molded bodies to produce the panel according to the invention. Subsequently, tear-off fabric and release films are placed. In the infusion of the liquid resin system can be used with flow aids and / or membrane films. The following variants are particularly preferred: i) use of a flow aid on only one side of the structure, and / or ii) use of a flow aid on both sides of the structure, and / or iii) construction with a semipermeable membrane (VAP structure) is preferably draped over the molded body on the flow aids, release film and Abreißgewebe be used on one or both sides and the semipermeable membrane is sealed by vacuum sealing tape to the mold surface, the Absaugvlies is used on the molding foreign side of the semipermeable membrane whereby the air surface is evacuated to the top, and / or iv) Use of a membrane bag vacuum bag, which is preferably placed on the opposite sprue side of the molded body, evacuating the air from the opposite side to the gate.
Der Aufbau wird anschließend mit Angüssen für das Harzsystem und Anschlüssen für die Evakuierung ausgestattet. Schließlich wird eine Vakuumfolie über den gesamten Aufbau aufgebracht, mit Dichtband abgedichtet und der gesamte Aufbau evakuiert. Nach der Infusion des Harzsystems findet unter Aufrechterhaltung des Vakuums die Reaktion des Harzsystems statt. The assembly is then fitted with sprues for the resin system and ports for evacuation. Finally, a vacuum film is applied over the entire structure, sealed with sealing tape and evacuated the entire structure. After infusion of the resin system, the reaction of the resin system takes place while maintaining the vacuum.
Gegenstand der vorliegenden Erfindung ist außerdem die Verwendung des erfindungsgemäßen Formkörpers oder des erfindungsgemäßen Paneels für Rotorblätter, in Windenergieanlagen, im Transportsektor, im Bausektor, im Automobilbau, im Schiffsbau, im Schienenfahrzeugbau, für den Containerbau, für sanitäre Anlagen und/oder in der Luft- und Raumfahrt. The present invention furthermore relates to the use of the shaped body or the panel according to the invention for rotor blades, in wind turbines, in the transport sector, in the construction sector, in the automotive industry, in shipbuilding, in rail vehicle construction, for container construction, for sanitary facilities and / or in the aerospace industry. and space travel.
Nachfolgend wird die vorliegende Erfindung anhand von Beispielen verdeutlicht. Beispiele Hereinafter, the present invention will be clarified by way of examples. Examples
Beispiel 1 (Vergleichsbeispiel; Formkörper aus reaktiv hergestellten PU- Formschaumstoffen ohne Faserverstärkung) Es wurden die folgenden Komponenten eingesetzt: Example 1 Comparative Example: Moldings of Reactively Produced PU Molded Foams Without Fiber Reinforcement The following components were used:
Erste Komponente (K1 ): First component (K1):
K1 -1 : Mischung aus Diphenylmethandiisocyanat und Polymethylenphenylpolyisocyanat mit einem Isocyanatindex von 130 und einerK1 -1: Mixture of diphenylmethane diisocyanate and polymethylene phenyl polyisocyanate with an isocyanate index of 130 and a
Viskosität von 200 mPa · s bei 25 °C. (nach DIN 53019) Viscosity of 200 mPa · s at 25 ° C. (according to DIN 53019)
Zweite Komponente (K2): K2-1 : Saccharose/Glyzerin-basiertes Polypropylenoxid mit einer Funktionalität von 4,5, einem zahlenmittleren Molekulargewicht Mn von 515 g/mol und einer Viskosität von 8000 mPa · s bei 25 °C. Second component (K2): K2-1: sucrose / glycerine-based polypropylene oxide having a functionality of 4.5, a number average molecular weight M n of 515 g / mol and a viscosity of 8000 mPa · s at 25 ° C.
K2-2: Polypropylenoxid mit einer Funktionalität von 2, einem zahlenmittleren Molekulargewicht Mn von 1000 g/mol und einer Viskosität von 150 mPa · s beiK2-2: polypropylene oxide having a functionality of 2, a number average molecular weight M n of 1000 g / mol and a viscosity of 150 mPa · s
25 °C; K2-3: Pentaerythritol-basiertes Ethylenoxid mit einer Funktionalität von 4, einem zahlenmittleren Molekulargewicht Mn von 350 g/mol und einer Viskosität von 1000 mPa · s bei 25 °C; 25 ° C; K2-3: pentaerythritol-based ethylene oxide having a functionality of 4, a number average molecular weight M n of 350 g / mol and a viscosity of 1000 mPa · s at 25 ° C .;
K2-4: Phthalsäureanhydrid/Diethylenglycol-basiert mit einer Funktionalität von 2, einem zahlenmittleren Molekulargewicht Mn von 350 g/mol und einer Viskosität von 2500 mPa · s bei 25 °C. (nach DI N 53019) Katalysator: tertiäres aliphatisches Amin K2-4: phthalic anhydride / diethylene glycol-based with a functionality of 2, a number average molecular weight M n of 350 g / mol and a viscosity of 2500 mPa · s at 25 ° C. (according to DI N 53019) Catalyst: tertiary aliphatic amine
Weitere Additive: Further additives:
A-1 : Kettenverlängerer: Propylenglycol-basiert, gewichtsmittleres A-1: chain extender: propylene glycol based, weight average
Molekulargewicht Mw von 134 g/mol Molecular weight M w of 134 g / mol
A-2: Vernetzer: Glyzerin-basiert, gewichtsmittleres Molekulargewicht Mw von 94 g/mol A-3: Stabilisator: Siliconhaitiger Stabilisator für Polyurethanhartschaumstoff A-2: Crosslinker: Glycerol-based, weight-average molecular weight M w of 94 g / mol A-3: Stabilizer: Silicone-containing stabilizer for rigid polyurethane foam
Weitere Komponenten: Leitungswasser a) Herstellung der Formkörper aus reaktiv hergestelltem PU-Formschaumstoff Other components: tap water a) Production of moldings from reactively produced molded PU foam
Die Herstellung des erfindungsgemäßen Reaktivschaumstoffs aus Polyurethan erfolgt durch das diskontinuierliche Verschäumen der reaktiven Mischungen in einer Form. Hierzu werden die zweite Komponente (K2) sowie die weiteren Additive, der Katalysator und die weiteren Komponenten vorgelegt, die erste Komponente (K1 ) hinzugewogen und die Mischung bei Raumtemperatur mit einem geeigneten Rührwerk bei 1800 U/min im offenen Gefäß vermischt. Die Gewichtsanteile der Komponenten sind in Tabelle 1 angegeben. Die erhaltene reaktive Mischung wird anschließend in eine geeignet temperierte Form bei 45 °C eingetragen und ausgehärtet unter Erhalt eines Polyurethanhartschaumstoffs. Anschließend wird der erhaltene Polyurethanhartschaumstoff für die weitere Verarbeitung in die benötigte Form geschnitten. Die Grundgeometrie der erhaltenen Formkörper ist durch das formgebende Werkzeug vorgegeben und in der weiteren Beschreibung näher beschrieben. Tabelle 1 : Komponente Gewichtsanteile The preparation of the reactive polyurethane foam according to the invention is carried out by the discontinuous foaming of the reactive mixtures in a mold. For this purpose, the second component (K2) and the other additives, the catalyst and the other components are introduced, the first component (K1) is added and the mixture is mixed at room temperature with a suitable stirrer at 1800 U / min in an open vessel. The parts by weight of the components are given in Table 1. The resulting reactive mixture is then introduced into a suitably tempered mold at 45 ° C and cured to obtain a rigid polyurethane foam. Subsequently, the polyurethane rigid foam obtained is cut into the required shape for further processing. The basic geometry of the moldings obtained is given by the forming tool and described in more detail in the further description. Table 1 : Component parts by weight
K2-1 31,0  K2-1 31.0
K2-2 16,0  K2-2 16.0
K2-3 10,0  K2-3 10.0
K2-4 28,0  K2-4 28.0
A-l 10,0  A-10.0
A-2 3,0  A-2 3.0
A-3 2,0  A-3 2.0
Katalysator 0,75  Catalyst 0.75
Leitungswasser 3,0  Tap water 3.0
Kl-1 100,0 b) Harzaufnahme der Formkörper unter Ausbildung eines Paneels.  Kl-1 100.0 b) Resin absorption of the moldings to form a panel.
Für die Harzaufnahme werden Platten direkt nach der Herstellung mit geschlossener Oberfläche (V1 ) und nach spanender Entfernung der Oberfläche durch Hobeln (V2) verglichen. Geschlitzte Platten werden entweder durch entsprechende Formteilwerkzeuge beim Formschäumverfahren (V3) oder durch spanende Bearbeitung mittels Kreissägen aus Platten (V4) hergestellt. In beiden Fällen beträgt der Schlitzabstand längs und quer jeweils 30 mm. Die Schlitze werden nur auf einer Seite der Platte mit einer Schlitzbreite von 2 mm und einer Schlitztiefe von 19 mm eingebracht (Plattendicke von 20 mm). For resin uptake, panels are compared directly after fabrication with closed surface (V1) and after removal of the surface by planing (V2). Slotted plates are produced either by appropriate molding tools in the foam molding process (V3) or by machining by means of circular saws made of plates (V4). In both cases, the slot spacing is 30 mm longitudinally and transversely. The slits are placed only on one side of the slab with a slit width of 2 mm and a slit depth of 19 mm (slab thickness of 20 mm).
Zur Bestimmung der Harzaufnahme werden neben den eingesetzten Harzsystemen, dem Reaktivschaumstoff und Glasgelegen die folgende Hilfsmaterialien verwendet: Nylon Vakuumfolie, Vakuumdichtband, Nylon Fließhilfe, Polyolefin Trennfolie, Polyester Abreißgewebe sowie PTFE Membranfolie und Polyester Absaugvlies. Paneele, nachfolgend auch als Sandwichmaterialien bezeichnet, werden aus den Formkörpern durch Aufbringung faserverstärkter Decklagen mittels Vakuuminfusion hergestellt. An der Ober- und Unterseite der (faserverstärkten) Schaumstoffe werden je zwei Lagen Quadrax-Glasgelege (Roving: E-Glass SE1500, OCV; Textil: Saertex, isotropes Laminat [0 -45 90°45°] mit je 1200 g/m2) aufgebracht. Für die Bestimmung der Harzaufnahme wird zwischen dem Formkörper, nachfolgend auch als Kernmaterial bezeichnet, und dem Glasgelege, im Gegensatz zur standardmäßigen Herstellung der Paneele, eine Trennfolie eingelegt. Damit ist die Harzaufnahme des reinen Formkörpers bestimmbar. Auf den Glasgelegen werden beidseitig das Abreißgewebe und die Fließhilfen angebracht. Der Aufbau wird anschließend mit Angüssen für das Harzsystem und Anschlüssen für die Evakuierung ausgestattet. Schließlich wird eine Vakuumfolie über den gesamten Aufbau aufgebracht, mit Dichtband abgedichtet und der gesamte Aufbau evakuiert. Der Aufbau wird auf einem elektrisch beheizbaren Tisch mit einer Glasoberfläche vorbereitet. Als Harzsystem wird aminisch härtendes Epoxid verwendet (Harz: BASF Baxxores 5400, Härter: BASF Baxxodur 5440, Mischungsverhältnis und weitere Verarbeitung nach Datenblatt). Nach dem Mischen der beiden Komponenten wird das Harz für 10 min bei bis zu 20 mbar evakuiert. Bei einer Harztemperatur von 23 +/- 2 °C erfolgt die Infusion auf den vortemperierten Aufbau (Tischtemperatur: 35 °C). Durch anschließende Temperaturrampe von 0,3 K/min von 35 °C auf 75 °C und isothermer Aushärtung bei 75 °C für 6 h können Paneele hergestellt werden, die aus den Reaktivschaumstoffen und glasfaserverstärkten Decklagen bestehen. To determine the resin uptake, the following auxiliary materials are used in addition to the resin systems used, the reactive foam and glass gels: nylon vacuum film, vacuum sealing tape, nylon flow aid, polyolefin release film, polyester tear off fabric and PTFE membrane film and polyester absorbent nonwoven. Panels, also referred to below as sandwich materials, are produced from the moldings by applying fiber-reinforced cover layers by means of vacuum infusion. At the top and bottom of the (fiber-reinforced) foams are each two layers of Quadrax Glasgelege (Roving: E-Glass SE1500, OCV, textile: Saertex, isotropic laminate [0 -45 90 ° 45 °], each 1200 g / m 2 ) applied. For the determination of the resin absorption, a release film is inserted between the molded body, hereinafter also referred to as core material, and the glass scrim, in contrast to the standard production of the panels. Thus, the resin absorption of the pure molded body can be determined. On the glass shelves the tear-off fabric and the flow aids are attached on both sides. The assembly is then fitted with sprues for the resin system and ports for evacuation. Finally, a Applied vacuum film over the entire structure, sealed with sealing tape and evacuated the entire structure. The structure is prepared on an electrically heated table with a glass surface. The resin system used is amine hardening epoxy (resin: BASF Baxxores 5400, hardener: BASF Baxxodur 5440, mixing ratio and further processing according to data sheet). After mixing the two components, the resin is evacuated for 10 minutes at up to 20 mbar. At a resin temperature of 23 + / - 2 ° C, infusion takes place on the pre-tempered structure (table temperature: 35 ° C). By subsequent temperature ramp of 0.3 K / min from 35 ° C to 75 ° C and isothermal curing at 75 ° C for 6 h panels can be made, which consist of the reactive foams and glass fiber reinforced cover layers.
Zu Beginn werden die Formkörper nach ISO 845 (Stand Oktober 2009) vermessen, um die Rohdichte des Formkörpers zu erhalten. Nach dem Aushärten des Harzsystems werden die verarbeiteten Paneele besäumt, um überschüssige Harzansammlungen in den Randbereichen durch nicht passend anliegende Vakuumfolie zu eliminieren. At the beginning, the moldings are measured according to ISO 845 (as of October 2009) in order to obtain the density of the molded body. After curing of the resin system, the processed panels are trimmed to eliminate excess resin build-up in the marginal areas by improperly fitting vacuum foil.
Anschließend werden die Decklagen entfernt und die enthaltenen Formkörper erneut durch ISO 845 vermessen. Aus der Differenz der Dichten ergibt sich die absolute Harzaufnahme. Durch Multiplikation mit der Dicke des Formkörpers ergibt sich die entsprechende Harzaufnahme in kg/m2. Subsequently, the cover layers are removed and the moldings contained are measured again by ISO 845. The difference of the densities results in the absolute resin absorption. By multiplying by the thickness of the shaped body, the corresponding resin absorption results in kg / m 2 .
Die gezeigten Ergebnisse (siehe Tabelle 1 ) demonstrieren, dass die Harzaufnahme bei Formkörpern aus endkonturnah gefertigten PU-Formschaumstoffen deutlich reduziert werden kann. Folglich ergibt sich daraus eine reduzierte Dichte des Paneels. The results shown (see Table 1) demonstrate that the resin uptake of moldings can be significantly reduced from near-net-shape PU molded foams. Consequently, this results in a reduced density of the panel.
Tabelle 1 Table 1
Beispiel Material Geschlossene Harzaufnahme Example Material Closed resin holder
Oberfläche  surface
V1 Platte direkt nach Verarbeitung > 90% < 0.1 kg/m2 V1 plate directly after processing> 90% <0.1 kg / m 2
(geschlossene Oberfläche)  (closed surface)
V2 Platte nach spanender Entfernung der < 5% 0,4 kg/m2 V2 plate after removal of <5% 0.4 kg / m 2
Oberfläche  surface
V3 Geschlitzte Platte direkt nach > 90% 3,2 kg/m2 V3 Slotted plate directly after> 90% 3.2 kg / m 2
Verarbeitung  processing
V4 Geschlitzte Platte durch spanende < 5% 3,8 kg/m2 V4 slotted plate by cutting <5% 3.8 kg / m 2
Verarbeitung Beispiel 2 (Formkörper aus reaktiv hergestelltem PU-Formschaumstoff mit Faserverstärkung) processing Example 2 (Moldings of Reactively Produced PU Molded Foam with Fiber Reinforcement)
Um die Schälfestigkeit bei gleichzeitig geringer Harzaufnahme an der Oberfläche zu verbessern, werden die Versuche aus Beispiel 1 wiederholt, allerdings wird der Formkörper (Reaktivschaumstoff) zunächst teilweise mit Glasfasern (Rovings, S2- Glass, 400 tex, AGY) verstärkt. In order to improve the peel strength at the same time low resin absorption at the surface, the experiments of Example 1 are repeated, however, the molded body (reactive foam) is initially partially reinforced with glass fibers (rovings, S2-glass, 400 tex, AGY).
Die Glasfasern werden in Form von Rovings unter einem Winkel α von 45° in vier unterschiedlichen Raumrichtungen im Winkel ß zueinander eingebracht (0°, 90°, 180°, 270°). In allen Raumrichtungen wird eine identische Anzahl von Glasfasern eingebracht. Die Glasfasern sind in einem regulären rechteckigen Muster mit gleichen Abständen (a) eingebracht. In den Versuchen wird der Abstand von a = 10 mm bis zu a = 20 mm variiert. Daraus resultieren ca. 10,000 bis 40,000 Glasfaserrovings pro Quadratmeter. An beiden Seiten werden zusätzlich ca. 10 mm der Glasfasern an der Decklage an Überstand gelassen, um die Anbindung an die später eingebrachten Glasfasermatten als Decklagen zu verbessern. Die Faser bzw. Faserrovings werden durch einen kombinierten Näh- / Häkelprozess automatisiert eingebracht. Zunächst wird mit einer Hakennadel (Durchmesser ca. 0,80 mm) vollständig von der ersten Seite zur zweiten Seite des Partikelschaums durchgestochen. Auf der zweiten Seite wird ein Roving in den Haken der Hakennadel eingehängt und anschließend von der zweiten Seite durch die Nadel zurück zur ersten Seite des Reaktivschaumstoffs gezogen. Schließlich wird der Roving an der zweiten Seite abgeschnitten und an der Nadel die gebildetete Rovingschlaufe aufgeschnitten. Die Hakennadel ist somit bereit für den nächsten Vorgang. Insgesamt wurden 40 000 verstärkende Glasfaserelemente (Rovings) / m2 bei einem Abstand von 10 mm und 10 000 Glasfaserelemente / m2 bei einem Raster von a1=a2=20 mm eingebracht. The glass fibers are introduced in the form of rovings at an angle α of 45 ° in four different spatial directions at an angle β to each other (0 °, 90 °, 180 °, 270 °). In all spatial directions, an identical number of glass fibers is introduced. The glass fibers are placed in a regular rectangular pattern at equal intervals (a). In the experiments, the distance is varied from a = 10 mm to a = 20 mm. This results in approximately 10,000 to 40,000 fiber rovings per square meter. In addition, about 10 mm of the glass fibers are left on the cover layer on the supernatant on both sides in order to improve the connection to the glass fiber mats later introduced as cover layers. The fiber or fiber rovings are introduced automatically by a combined sewing / crochet process. First, a hook needle (diameter approx. 0.80 mm) is pierced completely from the first side to the second side of the particle foam. On the second side, a roving is hooked into the hook of the hook needle and then pulled from the second side through the needle back to the first side of the reactive foam. Finally, the roving on the second side is cut off and the formed roving loop is cut on the needle. The hook needle is thus ready for the next process. A total of 40,000 reinforcing fiber elements (rovings) / m 2 were introduced at a distance of 10 mm and 10 000 glass fiber elements / m 2 at a grid of a 1 = a 2 = 20 mm.
Anschließend werden Paneele aus den Formkörpern durch Aufbringung faserverstärkter Decklagen mittels Vakuuminfusion hergestellt wie vorstehend für Beispiel 1 beschrieben. Im Gegensatz zu Beispiel 1 wird zwischen dem Formkörper und den Glasgelegen keine Trennfolie eingebracht. Subsequently, panels are produced from the moldings by applying fiber-reinforced cover layers by means of vacuum infusion as described above for Example 1. In contrast to Example 1, no release film is introduced between the molding and the Glasgelegen.
Die Schälfestigkeit der Paneele wird mit Single cantilever beam (SCB)-Proben bestimmt. Die Dicke der Formkörper beträgt 20 mm, die Schichten (S1 ) bestehen aus jeweils ca. 2 mm dicken, quasiisotropen glasfaserverstärkten Epoxidharzschichten. Damit ergibt sich eine Dicke des Paneels von 24 mm. Die Proben werden in einer Zwick Z050 Zugprüfmaschine mit einer Geschwindigkeit von 5 mm/min geprüft, wobei jeder Probekörper mehrfach (3 bis 4 mal) be- und entlastet wird. Das Risswachstum bzw. der Zuwachs bei jedem Belastungszyklus (Aa) wird optisch ermittelt. Aus dem Kraft-Weg-Verlauf wird die Risswachstumsenergie (AU) ermittelt. Daraus wird die Risszähigkeit bzw. Schälfestigkeit ermittelt als The peel strength of the panels is determined with single cantilever beam (SCB) samples. The thickness of the moldings is 20 mm, the layers (S1) each consist of about 2 mm thick, quasi-isotropic glass fiber reinforced epoxy resin. This results in a thickness of the panel of 24 mm. The samples are tested in a Zwick Z050 tensile testing machine at a speed of 5 mm / min, whereby each test piece is loaded and unloaded several times (3 to 4 times). The crack growth or the increase in each load cycle (Aa) is determined optically. From the Force-displacement curve determines the crack growth energy (AU). From this, the fracture toughness or peel strength is determined as
AU mit B als Probenbreite. AU with B as sample width.
Tabelle 2 Table 2
Wie deutlich aus Tabelle 2 zu erkennen ist, kann durch die erfindungsgemäßen einen reaktiv hergestellten PU-Formschaumstoff enthaltenden Formteile mit integrierten Fasern die Schälfestigkeit in einem Paneel deutlich gesteigert werden (B7 bis B10). Die Faserverstärkung des Reaktivschaumstoffs erlaubt damit bei nahezu identischer Harzaufnahme der Oberfläche eine deutliche Erhöhung der Schälfestigkeit. Speziell hängt die Festigkeit nur noch geringfügig von der Oberflächenrauigkeit bzw. Vorbehandlung ab und ermöglich damit eine Entkopplung der beiden Optimierungsziele Schälfestigkeit und Harzaufnahme. As can be clearly seen from Table 2, the peel strength in a panel can be increased significantly (B7 to B10) by means of the moldings with integrated fibers comprising a reactively produced PU molded foam according to the invention. The fiber reinforcement of the reactive foam thus allows for a nearly identical resin absorption of the surface a significant increase in the peel strength. Specifically, the strength depends only slightly on the surface roughness or pretreatment and thus allows a decoupling of the two optimization goals peel strength and resin absorption.

Claims

Patentansprüche claims
1. Formkörper aus Reaktivschaumstoff, dadurch gekennzeichnet, dass mindestens eine Faser (F) sich mit einem Faserbereich (FB2) innerhalb des Formkörpers befindet und von dem Reaktivschaumstoff umschlossen ist, während ein Faserbereich (FB1 ) der Faser (F) aus einer ersten Seite des Formkörpers herausragt und ein Faserbereich (FB3) der Faser (F) aus einer zweiten Seite des Formkörpers herausragt, wobei der Reaktivschaumstoff nach einem Formschäumverfahren hergestellt ist, wobei die Faser (F) in einem Winkel α von 10 bis 70° relativ zur Dickenrichtung (d) des Formkörpers in den Reaktivschaumstoff eingebracht ist und wobei der Formkörper erhältlich ist nach einem Verfahren umfassend die Schritte a) bis f): a) gegebenenfalls Aufbringen von mindestens einer Schicht (S2) auf mindestens eine Seite des Reaktivschaumstoffs, b) Erzeugung von einem Loch je Faser (F) im Reaktivschaumstoff und gegebenenfalls der Schicht (S2), wobei sich das Loch von einer ersten Seite zu einer zweiten Seite des Reaktivschaumstoffs und gegebenenfalls durch die Schicht (S2) erstreckt, c) Bereitstellung von mindestens einer Faser (F) auf der zweiten Seite des Reaktivschaumstoffs, d) Durchführen einer Nadel von der ersten Seite des Reaktivschaumstoffs durch das Loch zur zweiten Seite des Reaktivschaumstoffs und gegebenenfalls Durchführen der Nadel durch die Schicht (S2), e) Befestigen von mindestens einer Faser (F) an der Nadel auf der zweiten Seite des Reaktivschaumstoffs, und f) Rückführen der Nadel samt Faser (F) durch das Loch, so dass die Faser (F) sich mit dem Faserbereich (FB2) innerhalb des Formkörpers befindet und von dem Reaktivschaumstoff umschlossen ist, während der Faserbereich (FB1 ) der Faser (F) aus einer ersten Seite des Formkörpers oder gegebenenfalls aus der Schicht (S2) herausragt und der Faserbereich (FB3) der Faser (F) aus einer zweiten Seite des Formkörpers herausragt. A shaped body of reactive foam, characterized in that at least one fiber (F) is located with a fiber region (FB2) within the shaped body and is enclosed by the reactive foam, while a fiber region (FB1) of the fiber (F) from a first side of the Shaped protruding body and a fiber portion (FB3) of the fiber (F) protrudes from a second side of the molded body, wherein the reactive foam is produced by a foam molding process, said fiber (F) at an angle α of 10 to 70 ° relative to the thickness direction (i.e. ) of the shaped body is introduced into the reactive foam and wherein the shaped body is obtainable by a process comprising the steps a) to f): a) optionally applying at least one layer (S2) to at least one side of the reactive foam, b) producing a hole each fiber (F) in the reactive foam and optionally the layer (S2), wherein the hole from a first side to a second Se c) providing at least one fiber (F) on the second side of the reactive foam, d) passing a needle from the first side of the reactive foam through the hole to the second side of the reactive foam and optionally passing the needle through the layer (S2), e) attaching at least one fiber (F) to the needle on the second side of the reactive foam, and f) returning the needle and fiber (F) through the hole such that the fiber (F) is located with the fiber region (FB2) within the molded body and is surrounded by the reactive foam, while the fiber region (FB1) of the fiber (F) protrudes from a first side of the shaped body or optionally from the layer (S2) and the fiber region (FB3) of the fiber (F) protrudes from a second side of the shaped body.
2. Formkörper gemäß Anspruch 1 , dadurch gekennzeichnet, dass das Formschäumverfahren die folgenden Schritte I) bis IV) umfasst: Bereitstellung einer reaktiven Mischung, die zumindest eine erste Komponente (K1 ) und zumindest eine zweite Komponente (K2) enthält, wobei die erste Komponente (K1 ) und die zweite Komponente (K2) miteinander reagieren können, 2. Shaped body according to claim 1, characterized in that the foam molding process comprises the following steps I) to IV): Providing a reactive mixture containing at least a first component (K1) and at least one second component (K2), wherein the first component (K1) and the second component (K2) can react with one another,
Injektion der in Schritt I) bereitgestellten reaktiven Mischung in ein formgebendes Werkzeug, Injection of the reactive mixture provided in step I) into a forming tool,
Expansion der reaktiven Mischung in dem formgebenden Werkzeug unter Erhalt eines expandierten Schaumstoffs und Expansion of the reactive mixture in the forming tool to obtain an expanded foam and
Entformen des in Schritt III) erhaltenen expandierten Schaumstoffs aus dem formgebenden Werkzeug unter Erhalt des Reaktivschaumstoffs. Removal of the obtained in step III) expanded foam from the forming tool to obtain the reactive foam.
3. Formkörper gemäß Anspruch 1 oder 2, dadurch gekennzeichnet, dass der Reaktivschaumstoff auf Basis eines Polyurethans, eines Polyharnstoffs oder eines Polyisocyanurats ist, bevorzugt ist der Reaktivschaumstoff auf Basis eines Polyurethans, eines Polyharnstoffs oder eines Polyisocyanurats, das jeweils nach einem3. Shaped body according to claim 1 or 2, characterized in that the reactive foam is based on a polyurethane, a polyurea or a polyisocyanurate, preferably the reactive foam based on a polyurethane, a polyurea or a polyisocyanurate, each after a
Formschäumverfahren gemäß Anspruch 2 hergestellt wird und bei dem die in Schritt I) bereitgestellte reaktive Mischung als erste Komponente (K1 ) mindestens ein Polyisocyanat, und als zweite Komponente (K2) mindestens eine Verbindung mit gegenüber Isocyanaten reaktiven Gruppen, sowie als weitere Komponente mindestens ein Treibmittel enthält. Form foaming process according to claim 2 is prepared and wherein the provided in step I) reactive mixture as the first component (K1) at least one polyisocyanate, and as the second component (K2) at least one compound with isocyanate-reactive groups, and as further component at least one blowing agent contains.
4. Formkörper gemäß einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die Oberfläche von mindestens einer Seite des Formkörpers mindestens eine Vertiefung aufweist, vorzugsweise ist die Vertiefung ein Schlitz oder ein Loch, mehr bevorzugt wird mindestens eine Vertiefung auf der Oberfläche von mindestens einer Seite des Formkörpers im Anschluss an die Durchführung von Schritt IV) gemäß Anspruch 2 erzeugt, und/oder die Gesamtoberfläche des Formkörpers zu mehr als 30 %, vorzugsweise zu mehr als 50 %, mehr bevorzugt zu mehr als 80 %, insbesondere zu mehr als 95 %, geschlossen ist, und/oder iii) der Reaktivschaumstoff eine Glasübergangstemperatur von mindestens 80 °C, bevorzugt von mindestens 1 10 °C und insbesondere von mindestens 130 °C, aufweist. 4. Shaped body according to one of claims 1 to 3, characterized in that the surface of at least one side of the shaped body has at least one recess, preferably, the recess is a slot or a hole, more preferably at least one recess on the surface of at least one Side of the molding after the implementation of step IV) according to claim 2, and / or the total surface of the molding to more than 30%, preferably more than 50%, more preferably more than 80%, in particular more than 95 %, closed, and / or iii) the reactive foam has a glass transition temperature of at least 80 ° C, preferably of at least 1 10 ° C and in particular of at least 130 ° C.
5. Formkörper gemäß einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass i) die Faser (F) eine einzelne Faser oder ein Faserbündel, vorzugsweise ein5. Shaped body according to one of claims 1 to 4, characterized in that i) the fiber (F) is a single fiber or a fiber bundle, preferably a
Faserbündel, ist, und/oder die Faser (F) eine organische, anorganische, metallische, keramische Faser oder eine Kombination daraus ist, bevorzugt eine polymere Faser, Basaltfaser, Glasfaser, Kohlenstofffaser oder Naturfaser, insbesondere bevorzugt eine Polyaramidfaser, Glasfaser, Basaltfaser oder Kohlenstofffaser ist; eine polymere Faser ist vorzugsweise eine Faser aus Polyester, Polyamid, Polyaramid, Polyethylen, Polyurethan, Polyvinylchlorid, Polyimid und/oder Polyamidimid; eine Naturfaser ist vorzugsweise eine Faser aus Sisal, Hanf, Flachs, Bambus, Kokos und/oder Jute, und/oder die Faser (F) als Faserbündel eingesetzt wird mit einer Anzahl von Einzelfasern pro Bündel von mindestens 10, bevorzugt 100 bis 100 000, besonders bevorzugt 300 bis 10 000 bei Glasfasern und 1 000 bis 50 000 bei Kohlenstofffasern, und insbesondere bevorzugt 500 bis 5 000 bei Glasfasern und 2 000 bis 20 000 bei Kohlenstofffasern, und/oder der Faserbereich (FB1 ) und der Faserbereich (FB3) jeweils unabhängig voneinander 1 bis 45 %, vorzugsweise 2 bis 40 %, besonders bevorzugt 5 bis 30 %, und der Faserbereich (FB2) 10 bis 98 %, vorzugsweise 20 bis 96 %, besonders bevorzugt 40 bis 90 %, der Gesamtlänge einer Faser (F) ausmachen, und/oder v) die Faser (F) in einem Winkel α von 30 bis 60 °, bevorzugt von 30 bis 50°, noch mehr bevorzugt von 30 bis 45°, insbesondere von 45°, relativ zur Dickenrichtung (d) des Formkörpers in den Reaktivschaumstoff eingebracht ist, und/oder vi) im Formkörper die erste Seite des Formkörpers, aus der der FaserbereichFiber bundle is, and / or the fiber (F) is an organic, inorganic, metallic, ceramic fiber or a combination thereof, preferably a polymeric fiber, basalt fiber, glass fiber, carbon fiber or natural fiber, particularly preferably a polyaramid fiber, glass fiber, basalt fiber or carbon fiber is; a polymeric fiber is preferably a fiber of polyester, polyamide, polyaramide, polyethylene, polyurethane, polyvinyl chloride, polyimide and / or polyamide-imide; a natural fiber is preferably a fiber of sisal, hemp, flax, bamboo, coconut and / or jute, and / or the fiber (F) is used as a fiber bundle with a number of individual fibers per bundle of at least 10, preferably 100 to 100 000, particularly preferably 300 to 10,000 in glass fibers and 1,000 to 50,000 in carbon fibers, and more preferably 500 to 5,000 in glass fibers and 2,000 to 20,000 in carbon fibers, and / or the fiber region (FB1) and the fiber region (FB3), respectively independently of one another 1 to 45%, preferably 2 to 40%, particularly preferably 5 to 30%, and the fiber region (FB2) 10 to 98%, preferably 20 to 96%, particularly preferably 40 to 90%, of the total length of a fiber (F ), and / or v) the fiber (F) at an angle α of 30 to 60 °, preferably of 30 to 50 °, more preferably of 30 to 45 °, in particular of 45 °, relative to the thickness direction (d) of the shaped body is introduced into the reactive foam, and / or vi) in Shaped body the first side of the molding, from which the fiber area
(FB1 ) der Faser (F) herausragt, der zweiten Seite des Formkörpers, aus der der Faserbereich (FB3) der Faser (F) herausragt, gegenüberliegt, und/oder der Formkörper eine Vielzahl von Fasern (F), vorzugsweise von Faserbündeln, enthält und/oder mehr als 10 Fasern (F) oder Faserbündel pro m2 umfasst, bevorzugt mehr als 1 000 pro m2, besonders bevorzugt 4 000 bis 40 000 pro m2. (FB1) of the fiber (F) protrudes, the second side of the molded article from which the fiber region (FB3) of the fiber (F) protrudes, and / or the molded article contains a plurality of fibers (F), preferably fiber bundles and / or more than 10 fibers (F) or fiber bundles per m 2 , preferably more than 1,000 per m 2 , more preferably 4,000 to 40,000 per m 2 .
Paneel umfassend mindestens einen Formkörper gemäß einem der Ansprüche 1 bis 5 und mindestens eine Schicht (S1 ). Panel comprising at least one shaped body according to one of claims 1 to 5 and at least one layer (S1).
Paneel gemäß Anspruch 6, dadurch gekennzeichnet, dass die Schicht (S1 ) mindestens ein Harz umfasst, vorzugsweise ist das Harz ein reaktives duroplastisches oder thermoplastisches Harz, mehr bevorzugt ist das Harz auf der Basis von Epoxiden, Acrylaten, Polyurethanen, Polyamiden, Polyestern, ungesättigten Polyestern, Vinylestern oder Mischungen daraus, insbesondere ist das Harz ein aminisch härtendes Epoxidharz, ein latent härtendes Epixidharz, ein anhydridisch härtendes Epoxidharz oder ein Polyurethan aus Isocyanaten und Polyolen. Panel according to claim 6, characterized in that the layer (S1) comprises at least one resin, preferably the resin is a reactive thermosetting or thermoplastic resin, more preferably the resin is based on epoxides, acrylates, polyurethanes, polyamides, polyesters, unsaturated ones Polyesters, vinyl esters or mixtures thereof, in particular, the resin is an amine-curing epoxy resin, a latent curing epoxy resin, an anhydride-curing epoxy resin or a polyurethane of isocyanates and polyols.
Paneel gemäß Anspruch 7, dadurch gekennzeichnet, dass die Schicht (S1 ) zusätzlich mindestens ein faserförmiges Material enthält, wobei das faserförmige Material Fasern in Form von ein oder mehreren Lagen aus Schnittfasern, Vliesen, Gelegen, Gestricken und/oder Geweben, bevorzugt in Form von Gelegen oder Geweben, besonders bevorzugt in Form von Gelegen oder Geweben mit einem Flächengewicht pro Gelege bzw. Gewebe von 150 bis 2500 g/m2 enthält, und/oder das faserförmige Material organische, anorganische, metallische oder keramische Fasern, bevorzugt polymere Fasern, Basaltfasern, Glasfasern, Kohlenstofffasern oder Naturfasern, besonders bevorzugt Glasfasern oder Kohlenstofffasern enthält. A panel according to claim 7, characterized in that the layer (S1) additionally contains at least one fibrous material, the fibrous material comprising fibers in the form of one or more layers of cut fibers, nonwovens, layers, knits and / or fabrics, preferably in the form of Laid or woven fabrics, particularly preferably in the form of loops or fabrics having a basis weight per fabric of 150 to 2500 g / m 2 , and / or the fibrous material are organic, inorganic, metallic or ceramic fibers, preferably polymeric fibers, basalt fibers , Glass fibers, carbon fibers or natural fibers, particularly preferably glass fibers or carbon fibers.
30 9. Paneel gemäß einem der Ansprüche 6 bis 8, dadurch gekennzeichnet, dass das Paneel zwei Schichten (S1 ) aufweist und die beiden Schichten (S1 ) jeweils an einer Seite des Formkörpers angebracht sind, die der jeweils anderen Seite im Formkörper gegenüberliegt. Panel according to any one of claims 6 to 8, characterized in that the panel has two layers (S1) and the two layers (S1) are respectively attached to one side of the shaped body opposite to the other side in the molding.
35 10. Paneel gemäß einem der Ansprüche 6 bis 9, dadurch gekennzeichnet, dass i) der Faserbereich (FB1 ) der Faser (F) teilweise oder vollständig, vorzugsweise vollständig, mit der ersten Schicht (S1 ) in Kontakt ist, und/oder 10. panel according to one of claims 6 to 9, characterized in that i) the fiber region (FB1) of the fiber (F) partially or completely, preferably completely, in contact with the first layer (S1), and / or
40 ii) der Faserbereich (FB3) der Faser (F) teilweise oder vollständig, vorzugsweise vollständig, mit der zweiten Schicht (S1 ) in Kontakt ist, und/oder iii) das Paneel zwischen mindestens einer Seite des Formkörpers und mindestens einer Schicht (S1 ) mindestens eine Schicht (S2) aufweist, vorzugsweise ist die Schicht (S2) aus flächigen Fasermaterialien oder polymeren Folien, besonders bevorzugt aus porösen flächigen Fasermaterialien oder porösen polymeren Folien, insbesondere bevorzugt aus Papier, Glasfasern oder Kohlenstofffasern in Form von Vliesen,40 ii) the fiber region (FB3) of the fiber (F) is partially or completely, preferably completely, in contact with the second layer (S1), and / or iii) the panel is interposed between at least one side of the molded article and at least one layer (S1) at least one layer (S2), preferably, the layer (S2) of sheet-like fiber materials or polymeric films, more preferably of porous sheet-like fiber materials or porous polymeric films, particularly preferably of paper, glass fibers or carbon fibers in the form of nonwovens,
Gelegen oder Geweben. Paneel gemäß einem der Ansprüche 6 bis 10, dadurch gekennzeichnet, dass der im Paneel enthaltene Formkörper mindestens eine Seite enthält, die nicht mechanisch und/oder thermisch bearbeitet wurde, und/oder ii) der im Paneel enthaltene Formkörper mindestens eine Schicht (S2) aufweist, die im Formschäumverfahren gemäß Anspruch 2 in Schritt I I) als Trägerfolie auf den Reaktivschaumstoff aufgebracht wurde, und/oder iii) die mindestens eine Schicht (S1 ) ein Harz umfasst und der Reaktivschaumstoff des Formkörpers eine Harzaufnahme von weniger als 1000 g/m2, bevorzugt von weniger als 500 g/m2, besonders bevorzugt von weniger als 100 g/m2 aufweist, und/oder iv) das Paneel eine Schälfestigkeit von mehr als 200 J/m2, bevorzugt von mehr als 500 J/m2, besonders bevorzugt von mehr als 2000 J/m2 aufweist, und/oder v) der Reaktivschaumstoff des im Paneel enthaltenen Formkörpers eine spezifische Scherfestigkeit, gemessen parallel zu der mindestens einen Schicht (S1 ) im Bereich von 2 bis 25 kPa/(kg/m3), bevorzugt im Bereich von 3 bis 15 kPa/(kg/m3), besonders bevorzugt im Bereich von 4 bis 12 kPa/(kg/m3) aufweist, und/oder vi) der Reaktivschaumstoff des im Paneel enthaltenen Formkörpers ein Schubmodul gemessen parallel zu der mindestens einen Schicht (S1 ) im Bereich von 0,05 bis 0,6 MPa/(kg/m3), bevorzugt im Bereich von 0,05 bis 0,5 MPa/(kg/m3), besonders bevorzugt im Bereich vonLocated or tissues. Panel according to one of claims 6 to 10, characterized in that the molding contained in the panel contains at least one side which has not been mechanically and / or thermally processed, and / or ii) the molding contained in the panel at least one layer (S2) (iii) the at least one layer (S1) comprises a resin and the reactive foam of the shaped body comprises a resin uptake of less than 1000 g / m 2 , in the foam molding process according to claim 2 in step II) as carrier film on the reactive foam preferably of less than 500 g / m 2 , more preferably of less than 100 g / m 2 , and / or iv) the panel has a peel strength of more than 200 J / m 2 , preferably more than 500 J / m 2 , particularly preferably greater than 2000 J / m 2 , and / or v) the reactive foam of the molding contained in the panel has a specific shear strength, measured parallel to the at least one layer (S1) in the range from 2 to 25 kPa / (kg / m 3 ), preferably in the range of 3 to 15 kPa / (kg / m 3 ), more preferably in the range of 4 to 12 kPa / (kg / m 3 ), and / or vi) the reactive foam of the molding contained in the panel a shear modulus measured parallel to the at least one layer (S1) in the range of 0.05 to 0.6 MPa / (kg / m 3 ), preferably in the range of 0.05 to 0, 5 MPa / (kg / m 3 ), more preferably in the range of
0,05 bis 0,2 MPa/(kg/m3) aufweist, und/oder der im Paneel enthaltene Formkörper im Paneel eine spezifische Scherfestigkeit gemessen parallel zu der mindestens einen Schicht (S1 ) von mindestens 5 kPa/(kg/m3), bevorzugt von mindestens 8 kPa/(kg/m3), besonders bevorzugt von mindestens 12 kPa/(kg/m3) aufweist, und/oder der im Paneel enthaltene Formkörper im Paneel ein Schubmodul gemessen parallel zu der mindestens einen Schicht (S1 ) von mindestens 0,2 MPa/(kg/m3), bevorzugt von mindestens 0,6 MPa/(kg/m3), besonders bevorzugt von mindestens 1 ,0 MPa/(kg/m3), aufweist. 0.05 to 0.2 MPa / (kg / m 3 ), and / or the panel contained in the panel has a specific shear strength measured parallel to the at least one layer (S1) of at least 5 kPa / (kg / m 3 ), preferably of at least 8 kPa / (kg / m 3 ), more preferably of at least 12 kPa / (kg / m 3 ), and / or the panel contained in the panel a shear modulus measured parallel to the at least one layer (S1) of at least 0.2 MPa / (kg / m 3 ), preferably at least 0 , 6 MPa / (kg / m 3 ), more preferably at least 1, 0 MPa / (kg / m 3 ).
Verfahren zur Herstellung eines Formkörpers gemäß einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass mindestens eine Faser (F) in den Reaktivschaumstoff teilweise eingebracht wird, wodurch sich die Faser (F) mit dem Faserbereich (FB2) innerhalb des Formkörpers befindet und von dem Reaktivschaumstoff umschlossen ist, während der Faserbereich (FB1 ) der Faser (F) aus einer ersten Seite des Formkörpers herausragt und der Faserbereich (FB3) der Faser (F) aus einer zweiten Seite des Formkörpers herausragt. Process for producing a shaped article according to one of claims 1 to 5, characterized in that at least one fiber (F) is partially introduced into the reactive foam, whereby the fiber (F) with the fiber region (FB2) is inside the shaped article and of the Reactive foam is enclosed, while the fiber region (FB1) of the fiber (F) protrudes from a first side of the shaped body and the fiber region (FB3) of the fiber (F) protrudes from a second side of the shaped body.
Verfahren gemäß Anspruch 12, dadurch gekennzeichnet, dass das teilweise Einbringen von mindestens einer Faser (F) in den Reaktivschaumstoff durch Einnähen unter Verwendung einer Nadel erfolgt, vorzugsweise erfolgt das teilweise Einbringen durch die Schritte a) bis f): a) gegebenenfalls Aufbringen von mindestens einer Schicht (S2) auf mindestens eine Seite des Reaktivschaumstoffs, b) Erzeugung von einem Loch je Faser (F) im Reaktivschaumstoff und gegebenenfalls der Schicht (S2), wobei sich das Loch von einer ersten Seite zu einer zweiten Seite des Reaktivschaumstoffs und gegebenenfalls durch die Schicht (S2) erstreckt, c) Bereitstellung von mindestens einer Faser (F) auf der zweiten Seite des Reaktivschaumstoffs, d) Durchführen einer Nadel von der ersten Seite des Reaktivschaumstoffs durch das Loch zur zweiten Seite des Reaktivschaumstoffs und gegebenenfalls Durchführen der Nadel durch die Schicht (S2), e) Befestigen von mindestens einer Faser (F) an der Nadel auf der zweiten Qoite des Reaktivschaumstoffs, und f) Rückführen der Nadel samt Faser (F) durch das Loch, so dass die Faser (F) sich mit dem Faserbereich (FB2) innerhalb des Formkörpers befindet und von dem Reaktivschaumstoff umschlossen ist, während der Faserbereich (FB1 ) der Faser (F) aus einer ersten Seite des Formkörpers oder gegebenenfalls aus der Schicht (S2) herausragt und der Faserbereich (FB3) der Faser (F) aus einer zweiten Seite des Formkörpers herausragt, besonders bevorzugt werden die Schritte b) und d) gleichzeitig durchgeführt. A method according to claim 12, characterized in that the partial introduction of at least one fiber (F) into the reactive foam by sewing using a needle, preferably the partial introduction through the steps a) to f) is carried out: a) optionally applying at least a layer (S2) on at least one side of the reactive foam, b) production of a hole per fiber (F) in the reactive foam and optionally the layer (S2), wherein the hole from a first side to a second side of the reactive foam and optionally c) providing at least one fiber (F) on the second side of the reactive foam; d) passing a needle from the first side of the reactive foam through the hole to the second side of the reactive foam and optionally passing the needle therethrough Layer (S2), e) attaching at least one fiber (F) to the needle on the second Q oi te of reactive foam, and f) returning the needle and fiber (F) through the hole such that the fiber (F) is within the molding with the fiber portion (FB2) and is enclosed by the reactive foam while the fiber portion (FB1) of the fiber (F) protrudes from a first side of the molding or optionally from the layer (S2) and the fiber region (FB3) of the fiber (F) protrudes from a second side of the molding, more preferably, the steps b) and d) are carried out simultaneously.
Verfahren gemäß Anspruch 12 oder 13, bei dem die Vertiefungen im Formkörper gemäß Anspruch 4 teilweise oder vollständig vor dem Einbringen von mindestens einer Faser (F) in den Reaktivschaumstoff eingebracht werden. A method according to claim 12 or 13, wherein the recesses are incorporated in the molding according to claim 4 partially or completely before the introduction of at least one fiber (F) in the reactive foam.
Verfahren zur Herstellung eines Paneels gemäß einem der Ansprüche 6 bis 1 1 , dadurch gekennzeichnet, dass die mindestens eine Schicht (S1 ) als reaktives, viskoses Harz auf einen Formkörper gemäß einem der Ansprüche 1 bis 5 erzeugt, aufgebracht und ausgehärtet wird, vorzugsweise durch Flüssigimprägnierverfahren, besonders bevorzugt durch druck- bzw. vakuumunterstützte Imprägnierverfahren, insbesondere bevorzugt durch Vakuuminfusion oder druckunterstützte Injektionsverfahren, am meisten bevorzugt durch Vakuuminfusion. Process for producing a panel according to one of Claims 6 to 11, characterized in that the at least one layer (S1) is produced, applied and cured as a reactive, viscous resin on a molding according to one of Claims 1 to 5, preferably by liquid impregnation methods , more preferably by pressure- or vacuum-assisted impregnation methods, particularly preferably by vacuum infusion or pressure-assisted injection methods, most preferably by vacuum infusion.
Verwendung eines Formkörpers gemäß einem der Ansprüche 1 bis 5 oder eines Paneels gemäß einem der Ansprüche 6 bis 1 1 für Rotorblätter in Windenergieanlagen, im Transportsektor, im Bausektor, im Automobilbau, im Schiffsbau, im Schienenfahrzeugbau, für den Containerbau, für sanitäre Anlagen und/oder in der Luft- und Raumfahrt. Use of a shaped article according to one of claims 1 to 5 or a panel according to one of claims 6 to 11 for rotor blades in wind turbines, in the transport sector, in the construction sector, in the automotive industry, in shipbuilding, in rail vehicle construction, for container construction, for sanitary facilities and / or in the aerospace industry.
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US20200317880A1 (en) 2020-10-08
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US11613620B2 (en) 2023-03-28
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